JP6441307B2 - Interlayer film for laminated glass - Google Patents

Description

  The present invention relates to an interlayer film for laminated glass. The present invention also relates to a laminated glass using the interlayer film for laminated glass.

  A structure imparted with light diffusibility by adding fine particles has a function of diffusing light emitted from a point light source such as a light bulb or LED, or a line light source such as a fluorescent tube, and emitting light in a plane direction. The structure has been widely used as a backlight light source for liquid crystal display devices in the past, but in recent years there has been an increase in the use of the structure for other purposes. For example, it can be used as a light-shielding plate that also serves as a window material that uses transparency when the light source is turned off and becomes opaque due to diffused light in the surface direction when the light source is turned on. Can be mentioned. Specifically, a structure obtained by adding fine particles to a plate-like body made of an acrylic resin, a polycarbonate resin, or the like, or surface-treating the structure is widely used.

  As a member constituting the light shielding plate and the light emitting plate, a glass plate may be used together with an acrylic resin, a polycarbonate resin, or the like for reasons such as high scratch resistance, resistance to static electricity, and adhesion of dust. For example, a transmission type screen using a laminated glass using an interlayer film containing spherical fine particles satisfying specific regulations as well as a Fresnel lens sheet / lenticular sheet made of acrylic resin or the like as a light diffusion sheet (see Patent Document 1). ). Examples of the material constituting the intermediate film include polyvinyl acetal typified by polyvinyl butyral. As another example of laminated glass using diffused light, laminated glass that transmits visible light to some extent through a laminated glass in which a plurality of glass plates are bonded with an intermediate film containing titanium oxide fine particles but does not allow humans or objects to be visually recognized. (See Patent Document 2).

  On the other hand, an intermediate film made of polyvinyl acetal has, as a conventional problem, 1) easy to be colored by heating, 2) easily causes foreign matter (undissolved part), and 3) penetration resistance when used in safety laminated glass. There was a problem such as being easily lowered. When the problems 1) and 2) occur, the shades of the light-shielding plate and the light-emitting plate may change or uniform light diffusivity may not be obtained. When the problem 3) occurs, the safety of the laminated glass may be impaired. Various proposals have been made to solve these problems. For example, Patent Documents 3 and 4 describe a method for suppressing coloring of polyvinyl acetal by acetalization at a specific hydroxide ion concentration under high temperature and high pressure. Patent Document 5 describes a method of suppressing coloring of the obtained polyvinyl acetal by adding a reducing agent after neutralization by acetalization reaction. However, in the case of the methods described in Patent Documents 3 to 5, the obtained intermediate film made of polyvinyl acetal was easily colored by heating, and foreign matters were easily generated. Moreover, when the said intermediate film was used for safety laminated glass, penetration resistance was easy to fall.

  In order to obtain a light-shielding plate or light-emitting plate having uniform light diffusibility, it is necessary to highly disperse fine particles imparting light diffusibility in an intermediate film made of polyvinyl acetal. Patent Document 6 describes a method of dispersing inorganic fine particles in an intermediate film made of polyvinyl acetal by adding acid-modified polyolefin. However, in the case of the method described in Patent Document 6, there is still room for improvement in the dispersibility of the fine particles in the intermediate film made of polyvinyl acetal. For these reasons, an interlayer film for laminated glass made of polyvinyl acetal, in which all the above-mentioned problems are solved, is strongly demanded.

JP 2007-57906 A International Publication No. 2009/035081 JP 2011-219670 A JP 2011-219671 A Japanese Patent Laid-Open No. 05-140211 JP 2009-221029 A

  The present invention has been made to solve the above-mentioned problems, and is an intermediate for laminated glass containing polyvinyl acetal in which coloring due to heating and foreign matters (undissolved content) are small, and light diffusing fine particles are not aggregated and dispersed. The object is to provide a membrane. Furthermore, it aims at providing the laminated glass excellent in penetration resistance, transparency, and light diffusibility.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following inventions [1] to [13].
That is, the present invention
[1] An interlayer film for laminated glass containing polyvinyl acetal, wherein the degree of acetalization is 60 to 80 mol%, the content of vinyl ester monomer units is 0.1 to 20 mol%, and the viscosity average polymerization degree is Comprising a composition containing polyvinyl acetal of 1400 to 4000 and light diffusing fine particles, the difference between the refractive index of the light diffusing fine particles and the refractive index of the composition obtained by removing the light diffusing fine particles from the composition The absolute value is 0.20 or more, and the haze measured by a method according to JIS K 7105 when the laminated glass interlayer film is sandwiched between two 3 mm thick glass plates to form a laminated glass is 20 % Of the interlayer film for laminated glass satisfying the following formulas (1) and (2).
(AB) / A <0.80 (1)
1.00 × 10 ⁻² <(b / y) / (a / x) <2.00 × 10 ⁻¹ (2)
In the formula, A, a, B, b, x, and y are as follows.
A: Polymer component measured by a differential refractive index detector when the interlayer film for laminated glass heated at 230 ° C. for 3 hours is measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC). Peak top molecular weight a: Signal intensity at peak top molecular weight (A) B: Measured with an absorptiometric detector (measurement wavelength 280 nm) when GPC measurement is performed on the interlayer film for laminated glass heated at 230 ° C. for 3 hours. Peak top molecular weight b: Signal intensity at peak top molecular weight (B) x: Differential refractive index detection when GPC measurement of monodisperse polymethyl methacrylate (hereinafter sometimes abbreviated as PMMA) Signal intensity at peak top molecular weight measured with a vessel y: G of monodispersed PMMA When the C measured signal intensity at the peak top molecular weight measured by spectrophotometric detector (measuring wavelength 220 nm) The present invention also
[2] Further, the present invention relates to the interlayer film for laminated glass of [1] that satisfies the following formulas (3) and (4).
(AC) / A <0.80 (3)
5.00 × 10 ⁻³ <(c / y) / (a / x) <7.00 × 10 ⁻² (4)
In the formula, A, a, C, c, x, and y are as follows.
A: Same as the above formula (1), a, x, y: Same as the above formula (2) C: Absorbance detector when GPC measurement is performed on the interlayer film for laminated glass heated at 230 ° C. for 3 hours ( The peak top molecular weight c of the polymer component measured at a measurement wavelength of 320 nm): the signal intensity at the peak top molecular weight (C).
[3] The interlayer film for laminated glass according to [1] or [2], wherein the polyvinyl acetal is polyvinyl butyral (hereinafter sometimes abbreviated as “PVB”);
[4] The interlayer film for laminated glass according to any one of [1] to [3], further containing a plasticizer;
[5] The interlayer film for laminated glass according to [4], which contains triethylene glycol-di-2-ethylhexanoate as a plasticizer;
[6] The interlayer film for laminated glass according to any one of [1] to [5], wherein the light diffusing fine particles are an inorganic compound;
[7] The interlayer film for laminated glass according to [6], wherein the inorganic compound is a metal oxide;
[8] The interlayer film for laminated glass according to [7], wherein the metal oxide is titanium oxide;
[9] The interlayer film for laminated glass according to [7], wherein the metal oxide is zinc oxide;
[10] The interlayer film for laminated glass according to any one of [6] to [9], wherein the content of the light diffusing fine particles is 0.001 to 0.040% by mass;
[11] Laminated glass obtained by bonding a plurality of glass plates using the interlayer film for laminated glass according to any one of [1] to [9];
[12] Polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”) is acetalized, the degree of acetalization is 60 to 80 mol%, the content of vinyl ester monomer units is 0.1 to 20 mol%, The method for producing an interlayer film for laminated glass according to any one of [1] to [10], wherein after obtaining a polyvinyl acetal having a viscosity average polymerization degree of 1400 to 4000, the polyvinyl acetal is melt-molded;
[13] A light diffusing plate having the laminated glass according to [11] as a configuration;
[14] A light emitting plate comprising the laminated glass according to [11];
[15] The present invention relates to a sunroof panel having the laminated glass as described in [11].

  ADVANTAGE OF THE INVENTION According to this invention, there can be provided the intermediate film for laminated glasses containing the polyvinyl acetal in which the coloring and the foreign material by heating are few, and the light diffusing fine particles are not aggregated but dispersed. Furthermore, the laminated glass excellent in penetration resistance, transparency, and light diffusibility can be provided.

In the interlayer film for laminated glass of the present invention, the relationship between the molecular weight and the value measured by the differential refractive index detector (RI), and the absorbance measured by the molecular weight and the absorbance detector (UV) (measurement wavelength 280 nm) It is an example of the graph which showed these relationships.

The interlayer film for laminated glass of the present invention is a polyvinyl acetal having an acetalization degree of 60 to 80 mol%, a vinyl ester monomer unit content of 0.1 to 20 mol%, and a viscosity average polymerization degree of 1400 to 4000. And an absolute value of a difference between the refractive index of the light diffusing fine particles and the refractive index of the composition obtained by removing the light diffusing fine particles from the composition is 0.20 or more. And the haze measured by a method in accordance with JIS K 7105 when sandwiching the interlayer film for laminated glass between two glass plates having a thickness of 3 mm to form laminated glass is 20% or less, and The expressions (1) and (2) are satisfied.
(AB) / A <0.80 (1)
1.00 × 10 ⁻² <(b / y) / (a / x) <2.00 × 10 ⁻¹ (2)
In the formula, A, a, B, b, x, and y are as follows.
A: Peak top molecular weight of polymer component measured by differential refractive index detector when GPC measurement is performed on the interlayer film for laminated glass heated at 230 ° C. for 3 hours: signal intensity B at peak top molecular weight (A) : Peak top molecular weight b of the polymer component measured by an absorptiometric detector (measurement wavelength 280 nm) when GPC measurement is performed on the interlayer film for laminated glass heated at 230 ° C. for 3 hours: in peak top molecular weight (B) Signal intensity x: Signal intensity at peak top molecular weight measured by differential refractive index detector when monodispersed PMMA is measured by GPC y: Absorbance detector (measurement wavelength 220 nm when the monodispersed PMMA is measured by GPC) ) Signal intensity at peak top molecular weight measured in

However, in GPC measurement of interlayer film for laminated glass and monodisperse PMMA,
Mobile phase: 20 mmol / l sodium trifluoroacetate-containing hexafluoroisopropanol (hereinafter, hexafluoroisopropanol is abbreviated as HFIP)
Sample concentration: 1.00 mg / ml (solvent: 20 mmol / l HFIP containing sodium trifluoroacetate)
Sample injection volume: 100 μl
Column temperature: 40 ° C
Flow rate: 1.0 ml / min.

  In the GPC measurement in the present invention, a GPC apparatus having a differential refractive index detector and an absorptiometric detector and capable of simultaneously performing measurement by these detectors is used. The cell of the detection part of the absorptiometric detector preferably has a cell length (optical path length) of 10 mm. The absorptiometric detector may measure the absorption of ultraviolet light having a specific wavelength, or may measure the absorption of ultraviolet light having a specific range of wavelengths. The interlayer film for laminated glass subjected to the measurement is separated into each molecular weight component by a GPC column. The signal intensity by the differential refractive index detector is approximately proportional to the concentration (g / l) of the component constituting the interlayer film for laminated glass. On the other hand, the components detected by the absorptiometric detector are only those having a structure that absorbs a predetermined wavelength. By the GPC measurement, the concentration and absorbance at a predetermined wavelength of each molecular weight component of the interlayer film for laminated glass can be measured.

  HFIP containing sodium trifluoroacetate having a concentration of 20 mmol / l is used as the solvent and mobile phase used for dissolving the interlayer film for laminated glass and monodispersed PMMA measured in the GPC measurement. HFIP can dissolve the interlayer film for laminated glass and PMMA of the present invention. Further, by adding sodium trifluoroacetate, adsorption of components of the interlayer film for laminated glass and PMMA to the column filler is prevented. The flow rate and column temperature in the GPC measurement are appropriately adjusted according to the type of column used. The flow rate in the GPC measurement is usually 1.0 ml / min, and the column temperature is usually 40 ° C.

  The GPC column used in the said GPC measurement will not be specifically limited if the component in the intermediate film for laminated glasses of this invention can isolate | separate for every molecular weight. Specifically, “GPC HFIP-806M” manufactured by Showa Denko KK is suitably used.

  In the present invention, the peak top molecular weight (A) and the peak top molecular weight (B) are determined by preparing a calibration curve. The calibration curve is prepared based on the GPC elution capacity of these monodispersed PMMAs and their molecular weights by measuring several types of monodispersed PMMA having different molecular weights, which are used as standards for preparing the calibration curve. In the present invention, a calibration curve prepared using the detector is used for the measurement with the differential refractive index detector, and a calibration prepared using the detector (measurement wavelength: 220 nm) for the measurement with the absorptiometric detector. Use lines. Using these calibration curves, the peak top molecular weight (A) and the peak top molecular weight (B) are determined by conversion from the GPC elution volume.

  Prior to the GPC measurement, the interlayer film for laminated glass is heated at 230 ° C. for 3 hours. In the present invention, the interlayer film for laminated glass is heated by the following method. Heating is performed by hot pressing the interlayer film for laminated glass at a pressure of 2 MPa and 230 ° C. for 3 hours. Thereby, the difference in the hue of the sample after the heat treatment is clearly reflected in the difference in the absorbance (that is, the signal intensity detected by the absorptiometric detector). The thickness of the interlayer film for laminated glass to be subjected to heating is usually 600 to 800 μm, and preferably about 760 μm, which is the thickness of the usual interlayer film for laminated glass.

  The heated interlayer film for laminated glass is dissolved in the above-described solvent (HFIP containing sodium trifluoroacetate) to obtain a measurement sample. The concentration of the measurement sample is 1.00 mg / ml, and the injection volume is 100 μl. However, when the viscosity average degree of polymerization of the polyvinyl acetal in the interlayer film for laminated glass exceeds 2400, the excluded volume increases, and therefore the measurement sample concentration may not be measured with good reproducibility at 1.00 mg / ml. In that case, an appropriately diluted sample (injection amount 100 μl) is used. The signal intensity detected by the absorptiometric detector and the differential refractive index detector is proportional to the concentration of the sample. Therefore, the concentration of the diluted sample and the actually measured signal intensity are used to convert each signal intensity when the concentration of the measurement sample is 1.00 mg / ml.

  FIG. 1 shows the relationship between the molecular weight obtained by GPC measurement of the interlayer film for laminated glass of the present invention and the signal intensity measured by the differential refractive index detector, and the molecular weight and the spectrophotometric detector (measurement wavelength 280 nm). It is an example of the graph which showed the relationship with the signal intensity | strength (absorbance) measured by (1). The GPC measurement in the present invention will be further described with reference to FIG. In FIG. 1, the chromatogram indicated by “RI” is a plot of the signal intensity measured by the differential refractive index detector against the molecular weight (horizontal axis) of the interlayer film component for laminated glass converted from the elution volume. It is. The peak seen in the chromatogram near the molecular weight of 100,000 (log (M) = 5.0) is the peak of the polymer component. In the present invention, the molecular weight at the peak position of such a polymer component is defined as the peak top molecular weight (A) of the polymer component, and the signal intensity at the peak top molecular weight (A) is defined as the signal intensity (a). Since the interlayer film for laminated glass of the present invention contains polyvinyl acetal having a viscosity average polymerization degree of 1400 to 4000, the peak top molecular weight (A) of the polymer component usually exceeds 3500. In addition, in FIG. 1, the peak seen in the molecular weight 1500 vicinity is a peak of a plasticizer in case the plasticizer is contained in the intermediate film for laminated glasses. When there are a plurality of peaks having a peak top molecular weight exceeding 3500 in the chromatogram, the molecular weight at the peak position having the highest peak height is defined as the peak top molecular weight (A).

  In FIG. 1, the chromatogram indicated by “UV” is a signal measured by an absorptiometric detector (measurement wavelength: 280 nm) with respect to the molecular weight (horizontal axis) of the component of the interlayer film for laminated glass converted from the elution volume. The intensity (absorbance) is plotted. The peak seen in the chromatogram near the molecular weight of 50,000 (log (M) = 4.7) is the peak of the polymer component. In the present invention, the molecular weight at the peak position of such a polymer component is defined as the peak top molecular weight (B) of the polymer component, and the signal intensity (absorbance) at the peak top molecular weight (B) is defined as the signal intensity (b). Since the interlayer film for laminated glass of the present invention contains polyvinyl acetal having a viscosity average polymerization degree of 1400 to 4000, the peak top molecular weight (B) of the polymer component usually exceeds 3500. When there are a plurality of peaks having a peak top molecular weight exceeding 3500 in the chromatogram, the molecular weight at the peak position having the highest peak height is defined as the peak top molecular weight (B).

The interlayer film for laminated glass of the present invention has a peak top molecular weight (A) of a polymer component measured by a differential refractive index detector and a spectrophotometric detector (measurement wavelength: 280 nm) when GPC measurement is performed by the method described above. The peak top molecular weight (B) of the polymer component measured by (1) satisfies the following formula (1).
(AB) / A <0.80 (1)

  The peak top molecular weight (A) is a value serving as an index of the molecular weight of the polymer component in the interlayer film for laminated glass. On the other hand, the peak top molecular weight (B) is derived from a component having absorption at 280 nm, which is present in the polymer component. Usually, since the peak top molecular weight (A) is larger than the peak top molecular weight (B), (AB) / A becomes a positive value. If the peak top molecular weight (B) increases, (AB) / A decreases, and if the peak top molecular weight (B) decreases, (AB) / A increases. That is, when (A−B) / A is large, it means that there are many components that absorb ultraviolet light having a wavelength of 280 nm in the low molecular weight component in the polymer component.

  When (A-B) / A is 0.80 or more, as described above, the component that absorbs ultraviolet light having a wavelength of 280 nm increases in the low molecular weight component. In this case, foreign matter in the interlayer film for laminated glass increases. Further, the color resistance of the interlayer film for laminated glass, the foreign matters (undissolved part) in the interlayer film for laminated glass and the performance regarding the penetration resistance of the laminated glass obtained using the interlayer film for laminated glass cannot be balanced. (A−B) / A is preferably less than 0.75, more preferably less than 0.70.

The interlayer film for laminated glass of the present invention satisfies the following formula (2).
1.00 × 10 ⁻² <(b / y) / (a / x) <2.00 × 10 ⁻¹ (2)

  In formula (2), a is the signal intensity measured by the differential refractive index detector at the peak top molecular weight (A) in the GPC measurement. b is the signal intensity (absorbance) measured with an absorptiometric detector (measurement wavelength 280 nm) at the peak top molecular weight (B).

  In formula (2), x is the signal intensity at the peak top molecular weight measured by the differential refractive index detector when monodisperse PMMA is measured by GPC. y is the signal intensity (absorbance) at the peak top molecular weight measured with an absorptiometric detector (measurement wavelength 220 nm) when the monodispersed PMMA is measured by GPC. The GPC measurement of monodispersed PMMA is performed by using the above-described interlayer film for laminated glass except that monodispersed PMMA is used instead of the heated interlayer film for laminated glass and the measurement wavelength of the spectrophotometric detector is changed to 220 nm. The same as the GPC measurement. The signal intensity (x) is obtained in the same manner as the signal intensity (a). The signal intensity (y) is obtained in the same manner as the signal intensity (b). As the monodispersed PMMA used for determining x and y, PMMA having a weight average molecular weight of about 85000 is preferable.

  (B / y) / (a / x) is an index of the content of a component having a structure that absorbs ultraviolet light having a wavelength of 280 nm in the polymer component of the interlayer film for laminated glass. When this value is large, it means that the content is large. As described above, the signal intensity by the differential refractive index detector is approximately proportional to the component concentration (g / l) of the interlayer film for laminated glass. On the other hand, what is detected by the absorptiometric detector is only the component having absorption at 280 nm which is the measurement wavelength, and the signal intensity (absorbance) by the absorptiometric detector is proportional to the concentration of the component having absorption at 280 nm. . Usually, the signal intensity of the differential refractive index detector is indicated by “millivolt”, and the signal intensity (absorbance) of the absorptiometric detector is indicated by “absorbance unit (AU)”.

  However, since the signal intensity (a) measured by the differential refractive index detector and the signal intensity (b) obtained by the absorptiometric detector differ depending on the model of the GPC apparatus and the measurement conditions, the ratio of both is simply compared. It ’s difficult. On the other hand, in the present invention, as described below, the ratio of the signal intensity obtained by the differential refractive index detector and the signal intensity obtained by the absorptiometric detector is not different depending on the model of the GPC apparatus and the measurement conditions. Desired.

  In the present invention, the ratio (a / x) of the signal intensity (a) of the interlayer film for laminated glass by the differential refractive index detector to the signal intensity (x) of monodispersed PMMA by the differential refractive index detector, and the spectrophotometric detection The ratio (b / y) of the signal intensity (b) of the interlayer film for laminated glass by the absorptiometric detector to the signal intensity (y) of monodispersed PMMA by the vessel is obtained. And ratio (b / y) / (a / x) of both is calculated | required and this is made into the parameter | index of content of the component which has a structure which absorbs ultraviolet light with a wavelength of 280 nm. Thus, by using the signal intensity of monodispersed PMMA as a reference, the same index can be used for evaluation regardless of the device model and measurement conditions.

The interlayer film for laminated glass of the present invention preferably satisfies the following formula (2 ′), and more preferably satisfies the following formula (2 ″).
1.50 × 10 ⁻² <(b / y) / (a / x) <1.50 × 10 ⁻¹ (2 ′)
2.00 × 10 ⁻² <(b / y) / (a / x) <1.00 × 10 ⁻¹ (2 ″)

When (b / y) / (a / x) is 1.00 × 10 ⁻² or less, as described above, the polymer component of the interlayer film for laminated glass has few components that absorb ultraviolet light having a wavelength of 280 nm. Therefore, foreign matter (undissolved part) in the interlayer film for laminated glass increases. Further, the color resistance of the interlayer film for laminated glass, the foreign matters (undissolved part) in the interlayer film for laminated glass and the performance regarding the penetration resistance of the laminated glass obtained using the interlayer film for laminated glass cannot be balanced. Conversely, when (b / y) / (a / x) is 2.00 × 10 ⁻¹ or more, the polymer component of the interlayer film for laminated glass has many components that absorb ultraviolet light having a wavelength of 280 nm. Therefore, the coloring resistance of the interlayer film for laminated glass and the penetration resistance of the obtained laminated glass are deteriorated.

From the viewpoint of excellent balance of the color resistance of the interlayer film for laminated glass, the foreign matter (undissolved part) in the interlayer film for laminated glass and the penetration resistance of the laminated glass obtained using the interlayer film for laminated glass, In the GPC measurement, the peak top molecular weight (A) measured with a differential refractive index detector and the peak top molecular weight (C) measured with an absorptiometric detector (measurement wavelength: 320 nm) are expressed by the following formula (3).
(AC) / A <0.80 (3)
It is preferable to satisfy.

  The peak top molecular weight (C) is measured in the same manner as the peak top molecular weight (B) except that the measurement wavelength in the absorptiometric detector is 320 nm. A peak top molecular weight (C) originates in the component which has absorption in 320 nm which exists in the polymer component in the intermediate film for laminated glasses. Usually, since the peak top molecular weight (A) is larger than the peak top molecular weight (C), (AC) / A becomes a positive value. If the peak top molecular weight (C) increases, (AC) / A decreases, and if the peak top molecular weight (C) decreases, (AC) / A increases. That is, when (AC) / A is large, it means that the low molecular weight component in the polymer component has many components that absorb ultraviolet rays having a wavelength of 320 nm.

  When (AC) / A is 0.80 or more, as described above, the component that absorbs ultraviolet light having a wavelength of 320 nm increases in the low molecular weight component. In this case, foreign matter in the interlayer film for laminated glass may increase. In addition, the anti-coloring property of the interlayer film for laminated glass, the foreign matter (undissolved part) in the interlayer film for laminated glass and the performance regarding the penetration resistance of the laminated glass obtained using the interlayer film for laminated glass may not be balanced. There is. (AC) / A is more preferably less than 0.75, and even more preferably less than 0.70.

The interlayer film for laminated glass of the present invention preferably satisfies the following formula (4).
5.00 × 10 ⁻³ <(c / y) / (a / x) <7.00 × 10 ⁻² (4)

  In the formula (4), a, x and y are the same as the above formula (2). c is the signal intensity (absorbance) measured with an absorptiometric detector (measurement wavelength: 320 nm) at the peak top molecular weight (C).

  Here, (c / y) / (a / x) is an index of the content of a component having a structure that absorbs ultraviolet light having a wavelength of 320 nm in the polymer component of the interlayer film for laminated glass. When this value is large, it means that the content is large. And it calculates | requires similarly to the above-mentioned (b / y) / (a / x) except the measurement wavelength in an absorptiometric detector being 320 nm.

The interlayer film for laminated glass of the present invention preferably satisfies the following formula (4 ′), and more preferably satisfies the following formula (4 ″).
7.00 × 10 ⁻³ <(c / y) / (a / x) <6.00 × 10 ⁻² (4 ′)
1.00 × 10 ⁻² <(c / y) / (a / x) <5.00 × 10 ⁻² (4 ″)

When (c / y) / (a / x) is 5.00 × 10 ⁻³ or less, as described above, the polymer component of the interlayer film for laminated glass has few components that absorb ultraviolet light having a wavelength of 320 nm. Therefore, there is a possibility that foreign matter in the interlayer film for laminated glass increases. In addition, the anti-coloring property of the interlayer film for laminated glass, the foreign matter (undissolved part) in the interlayer film for laminated glass and the performance regarding the penetration resistance of the laminated glass obtained using the interlayer film for laminated glass may not be balanced. There is. Conversely, when (c / y) / (a / x) is 7.00 × 10 ⁻² or more, the polymer component of the interlayer film for laminated glass has many components that absorb ultraviolet light having a wavelength of 320 nm. Therefore, the coloring resistance of the interlayer film for laminated glass and the penetration resistance of the obtained laminated glass may be deteriorated.

  The degree of acetalization of the polyvinyl acetal in the interlayer film for laminated glass of the present invention is 60 to 80 mol%. The degree of acetalization is preferably 62 to 78 mol%, more preferably 65 to 75 mol%. When the degree of acetalization is less than 60 mol%, the compatibility with a plasticizer or the like decreases. Moreover, the penetration resistance of the obtained laminated glass falls. On the other hand, when the degree of acetalization exceeds 80 mol%, the efficiency of the acetalization reaction is remarkably lowered, and therefore it is necessary to carry out the reaction at a high temperature for a long time. As a result, the penetration resistance of the obtained laminated glass is lowered, and the coloring resistance of the obtained interlayer film for laminated glass is lowered.

  The degree of acetalization represents the ratio of acetalized vinyl alcohol monomer units to all monomer units constituting polyvinyl acetal. Among the vinyl alcohol monomer units in the raw material polyvinyl alcohol (hereinafter sometimes abbreviated as PVA), those not acetalized remain as vinyl alcohol monomer units in the obtained polyvinyl acetal. To do.

The viscosity average polymerization degree of the polyvinyl acetal is represented by the viscosity average polymerization degree of the raw material PVA measured according to JIS K 6726. That is, after re-saponifying polyvinyl alcohol to a saponification degree of 99.5 mol% or more and purifying it, it can be obtained from the intrinsic viscosity [η] measured in water at 30 ° C. by the following equation. The viscosity average polymerization degree of PVA and the viscosity average polymerization degree of polyvinyl acetal obtained by acetalizing it are substantially the same.
P = ([η] × 10000 / 8.29) (1 / 0.62)

  The viscosity average polymerization degree of the polyvinyl acetal is 1400 to 4000, and preferably 1500 to 3000. When the viscosity average polymerization degree is less than 1400, the strength of the interlayer film for laminated glass is low, and the resulting laminated glass has insufficient penetration resistance. Conversely, when the degree of polymerization exceeds 4000, the melt viscosity becomes too high and film formation becomes difficult.

  The content of the vinyl ester monomer unit in the polyvinyl acetal is 0.1 to 20 mol%, preferably 0.3 to 18 mol%, more preferably 0.5 to 15 mol%, Preferably it is 0.7-13 mol%. When the content of the vinyl ester monomer unit is less than 0.1 mol%, the polyvinyl acetal cannot be stably produced and the film cannot be formed. On the other hand, when the content of the vinyl ester monomer unit exceeds 20 mol%, the interlayer film for laminated glass becomes highly colored.

  The content of monomer units other than acetalized monomer units, vinyl ester monomer units and vinyl alcohol monomer units in the polyvinyl acetal is preferably 20 mol% or less, more preferably 10%. It is less than mol%.

  The polyvinyl acetal is usually produced by acetalizing polyvinyl alcohol. Polyvinyl alcohol is usually produced by saponifying a polyvinyl ester.

  Polyvinyl esters are produced by polymerizing vinyl ester monomers. Examples of vinyl ester monomers used in the production of polyvinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate and versatic. Examples thereof include vinyl acid, and vinyl acetate is particularly preferable.

  Moreover, it originates in a thiol compound by polymerizing a vinyl ester monomer in presence of thiol compounds, such as 2-mercaptoethanol, n-dodecyl mercaptan, mercaptoacetic acid, 3-mercaptopropionic acid, and saponifying the obtained polyvinyl ester. A PVA having a functional group introduced at the end is obtained.

  Examples of the method for polymerizing the vinyl ester monomer include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In particular, a bulk polymerization method performed without a solvent or a solution polymerization method performed using a solvent such as alcohol is usually employed. In terms of enhancing the effect of the present invention, a solution polymerization method in which polymerization is performed together with a lower alcohol is preferable. The lower alcohol is not particularly limited, but an alcohol having 3 or less carbon atoms such as methanol, ethanol, propanol and isopropanol is preferable, and methanol is usually used. When performing the polymerization reaction by the bulk polymerization method or the solution polymerization method, the reaction can be carried out by either a batch method or a continuous method. Examples of the initiator used for the polymerization reaction include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl-valeronitrile), 2,2′-azobis (4-methoxy). -2,4-dimethylvaleronitrile) and other azo-based initiators; organic peroxide-based initiators such as benzoyl peroxide, n-propyl peroxycarbonate, peroxydicarbonate and the like, as long as the effects of the present invention are not impaired. A well-known initiator is mentioned. Among these, organic peroxide initiators having a half-life at 60 ° C. of 10 to 110 minutes are preferable, and it is particularly preferable to use peroxydicarbonate. Although there is no restriction | limiting in particular about the polymerization temperature at the time of performing a polymerization reaction, The range of 5 to 200 degreeC is suitable.

  When the vinyl ester monomer is polymerized, a copolymerizable monomer can be copolymerized as necessary as long as the effects of the present invention are not impaired. Such monomers include α-olefins such as ethylene, propylene, 1-butene, isobutene, 1-hexene; carboxylic acids such as fumaric acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride or the like Derivatives; acrylic acid or salts thereof; acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate; methacrylic acid or salts thereof; methyl methacrylate, ethyl methacrylate, n-methacrylate Methacrylic acid esters such as propyl and isopropyl methacrylate; Acrylamide derivatives such as acrylamide, N-methylacrylamide and N-ethylacrylamide; Methacrylamide derivatives such as methacrylamide, N-methylmethacrylamide and N-ethylmethacrylamide Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether; hydroxy group-containing vinyl ethers such as ethylene glycol vinyl ether, 1,3-propanediol vinyl ether, 1,4-butanediol vinyl ether; allyl Allyl ethers such as acetate, propyl allyl ether, butyl allyl ether, hexyl allyl ether; monomers having an oxyalkylene group; isopropenyl acetate, 3-buten-1-ol, 4-penten-1-ol, 5-hexene Hydroxy group-containing α-olefins such as -1-ol, 7-octen-1-ol, 9-decen-1-ol, 3-methyl-3-buten-1-ol; ethylene sulfonic acid Monomers having a sulfonic acid group such as allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid; vinyloxyethyltrimethylammonium chloride, vinyloxybutyltrimethylammonium chloride, vinyloxyethyldimethylamine, Single groups having a cationic group such as vinyloxymethyldiethylamine, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidodimethylamine, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, dimethylallylamine, and allylethylamine Mer: vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane Monomers having silyl groups such as vinyl triethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, 3- (meth) acrylamide-propyltrimethoxysilane, 3- (meth) acrylamide-propyltriethoxysilane Etc. The amount of the monomer that can be copolymerized with these vinyl ester monomers varies depending on the purpose and use of the monomer, but is usually based on all monomers used for copolymerization. Is 20 mol% or less, preferably 10 mol% or less.

  PVA is obtained by saponifying the polyvinyl ester obtained by the above-mentioned method in an alcohol solvent.

  The saponification degree of PVA used for the production of polyvinyl acetal is preferably 80 to 99.9 mol%, more preferably 82 to 99.7 mol%, still more preferably 85 to 99.5 mol%, particularly preferably. Is 87-99.3 mol%. When the degree of saponification of PVA is less than 80 mol%, the number of foreign matters (undissolved parts) in the interlayer film for laminated glass may increase, and the coloring resistance of the interlayer film may decrease. When the saponification degree exceeds 99.9 mol%, there is a possibility that PVA cannot be stably produced.

  PVA may contain an alkali metal salt of a carboxylic acid, and its content is preferably 0.50% by mass or less, more preferably 0.37% by mass or less, and 0.28% by mass in terms of the alkali metal mass. The following is more preferable, and 0.23 mass or less is particularly preferable. When content of the alkali metal salt of carboxylic acid in PVA exceeds 0.50 mass%, there exists a possibility that a laminated glass intermediate film may become easy to color. The content of alkali metal salt of carboxylic acid (calculated in terms of alkali metal mass) is obtained from the amount of alkali metal ions obtained by ashing PVA with a platinum crucible and then measuring the resulting ash content by ICP emission analysis. Can do.

  As the catalyst for the saponification reaction of the polyvinyl ester, an alkaline substance is usually used. Examples thereof include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal alkoxides such as sodium methoxide. The amount of the alkaline substance used is preferably within a range of 0.002 to 0.2 in a molar ratio based on the vinyl ester monomer unit of the polyvinyl ester, and within a range of 0.004 to 0.1. It is particularly preferred. The saponification catalyst may be added all at once in the early stage of the saponification reaction, or a part thereof may be added in the early stage of the saponification reaction, and the rest may be added during the saponification reaction.

  Examples of the solvent that can be used for the saponification reaction include methanol, methyl acetate, dimethyl sulfoxide, diethyl sulfoxide, dimethylformamide, and the like. Of these solvents, methanol is preferably used. In its use, the water content of methanol is preferably adjusted to 0.001 to 1% by weight, more preferably 0.003 to 0.9% by weight, and particularly preferably 0.005 to 0.8% by weight.

  The saponification reaction is preferably performed at a temperature of 5 to 80 ° C, more preferably 20 to 70 ° C. The time required for the saponification reaction is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. The saponification reaction can be carried out by either a batch method or a continuous method. After completion of the saponification reaction, the remaining saponification catalyst may be neutralized as necessary. Usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate.

  The alkaline substance containing an alkali metal added during the saponification reaction is usually neutralized by an ester such as methyl acetate produced by the progress of the saponification reaction, or neutralized by adding a carboxylic acid such as acetic acid. At this time, an alkali metal salt of a carboxylic acid such as sodium acetate is formed.

  In order to reduce the alkali metal salt, the PVA may be washed with a washing solution containing a lower alcohol such as methanol after saponification. The cleaning liquid may contain 20 parts by mass or less of water with respect to 100 parts by mass of the lower alcohol. Moreover, the said washing | cleaning liquid may contain ester, such as methyl acetate produced | generated in a saponification process. The content of the ester at this time is not particularly limited, but is preferably 1000 parts by mass or less with respect to 100 parts by mass of the lower alcohol. The addition amount of the cleaning liquid used for cleaning is preferably 100 parts by mass to 10,000 parts by mass, more preferably 150 parts by mass to 5000 parts by mass with respect to 100 parts by mass of the gel obtained by saponification and PVA swelled by alcohol. 200 mass parts-1000 mass parts are still more preferable. When the addition amount of the cleaning liquid is less than 100 parts by mass, the alkali metal salt amount of the carboxylic acid may exceed the above range. On the other hand, when the addition amount of the cleaning liquid exceeds 10,000 parts by mass, the improvement of the cleaning effect by increasing the addition amount cannot be expected. The washing method is not particularly limited. For example, PVA (swelled gel) and a washing solution are added to the tank, and the mixture is stirred or allowed to stand for 5 to 180 minutes at 5 to 100 ° C. to remove the liquid. A batch method in which the process is repeated until the content of the alkali metal salt of the carboxylic acid is within the above range is exemplified. Further, there is also a continuous method in which PVA is continuously added from the top of the tower at approximately the same temperature and for the same time as the batch method, and a cleaning liquid is continuously added from the bottom of the tower, and the two are brought into contact with each other.

  The alkali metal salt of the carboxylic acid that may be contained in PVA is obtained by neutralizing the alkali catalyst used in the saponification step described above, such as sodium hydroxide, potassium hydroxide, sodium methoxide, etc. with carboxylic acid. In addition, carboxylic acid added for the purpose of suppressing alcoholysis of vinyl ester monomers such as vinyl acetate used in the polymerization process is neutralized in the saponification process, radical polymerization is stopped When a carboxylic acid having a conjugated double bond is used as an inhibitor to be added, the carboxylic acid is obtained by neutralization in the saponification step, or is intentionally added. . Specific examples include sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium glycerate, potassium glycerate, sodium malate, potassium malate, sodium citrate, potassium citrate, sodium lactate, potassium lactate, tartaric acid Sodium, potassium tartrate, sodium salicylate, potassium salicylate, sodium malonate, potassium malonate, sodium succinate, potassium succinate, sodium maleate, potassium maleate, sodium phthalate, potassium phthalate, sodium oxalate, potassium oxalate , Sodium glutarate, potassium glutarate, sodium abietic acid, potassium abietic acid, sodium sorbate, potassium sorbate, 2,4,6-octatri Sodium -1-carboxylate, potassium 2,4,6-octatriene-1-carboxylate, sodium eleostearate, potassium eleostearate, sodium 2,4,6,8-decatetraene-1-carboxylate 2,4,6,8-decatetraene-1-carboxylate, sodium retinoate, potassium retinoate and the like, but are not limited thereto.

  The PVA thus obtained is acetalized to produce polyvinyl acetal used for the production of an interlayer film for laminated glass. Although the method of acetalization is not specifically limited, For example, the following method is mentioned. After heating to 80-100 degreeC and dissolving PVA in water, the 3-40 mass% aqueous solution of PVA is obtained by cooling slowly over 10-60 minutes. When the temperature falls to −10 to 30 ° C., an aldehyde and an acid catalyst are added to the aqueous solution, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant. At that time, polyvinyl acetal having reached a certain degree of acetalization is precipitated. Thereafter, the temperature of the reaction solution is raised to 25 to 80 ° C. over 30 to 300 minutes, and the temperature is maintained for 10 minutes to 25 hours (this temperature is set as the reaction temperature for driving in). Next, a neutralizing agent such as an alkali is added to the reaction solution as necessary to neutralize the acid catalyst, and the resultant is washed with water and dried to obtain polyvinyl acetal.

  In general, aggregated particles made of polyvinyl acetal are generated in such a reaction or processing step, and coarse particles are easily formed. When such coarse particles are generated, there is a risk of causing variation between batches. On the other hand, when a specific PVA described later is used as a raw material, the generation of coarse particles is suppressed from the conventional product, and as a result, foreign matter (undissolved content) is reduced when the resulting polyvinyl acetal is melt-formed. An interlayer film for laminated glass can be obtained.

  It does not specifically limit as an acid catalyst used for acetalization reaction, Any organic acid and inorganic acid can be used, For example, an acetic acid, paratoluenesulfonic acid, nitric acid, a sulfuric acid, hydrochloric acid etc. are mentioned. Of these, hydrochloric acid, sulfuric acid, and nitric acid are preferably used. In general, when nitric acid is used, the reaction rate of the acetalization reaction is increased, and improvement in productivity can be expected. On the other hand, the obtained polyvinyl acetal particles tend to be coarse and the variation between batches tends to increase. However, when a specific polyvinyl alcohol is used as a raw material, the formation of coarse particles is suppressed, and as a result, when the obtained polyvinyl acetal is melt-formed, the foreign matter (undissolved content) is reduced. An intermediate film can be obtained.

  Although the aldehyde used for the acetalization reaction of polyvinyl acetal is not particularly limited, a conventionally known aldehyde having 1 to 8 carbon atoms is preferable, an aldehyde having 4 to 6 carbon atoms is more preferable, and n-butyraldehyde is particularly preferable. In the present invention, polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.

  In the present invention, as a method of adjusting each value obtained by GPC measurement of the interlayer film for laminated glass so as to fall within the above-described range, 1) a method of forming a film by adding an antioxidant to polyvinyl acetal, 2 ) A method of using a specific PVA as a raw material for polyvinyl acetal used for the production of an interlayer film for laminated glass. You may combine these methods suitably.

  The antioxidant used in the method 1) is not particularly limited, and examples thereof include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Among these, phenolic antioxidants are used. Preferably, alkyl-substituted phenolic antioxidants are particularly preferred.

  Examples of the phenolic antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and 2,4-di-t-amyl-6. Acrylate compounds such as-(1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t- Butyl-4-ethylphenol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4, 4'-butylidene-bis (4-methyl-6-t-butylphenol), 4,4'-butylidene-bis (6-t-butyl-m-cresol), 4,4'-thiobis 3-methyl-6-tert-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-) 5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,3-tris (2-methyl-4-hydroxy -5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate) methane, triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-) 3,5-dimethylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3-methyl-5-t-butylanilino) -2,4-bis-octylthio Triazine group-containing phenolic compounds such as -1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine There is.

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2-t-butyl). -4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, 9,10-dihydro-9-oxa-10-phos Faphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9 , 10-Dihydro-9-oxa-10-phosphaf Monophosphite compounds such as nanthrene; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-ditridecylphosphite), 4,4′-isopropylidene-bis (phenyl-dialkyl (C12 ~ C15) phosphite), 4,4'-isopropylidene-bis (diphenylmonoalkyl (C12-C15) phosphite), 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5- and diphosphite compounds such as t-butylphenyl) butane and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene phosphite. Of these, monophosphite compounds are preferred.

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, pentaerythritol-tetrakis- (Β-lauryl-thiopropionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane.

  These antioxidants can be used alone or in combination of two or more. Although the compounding quantity of antioxidant has no restriction | limiting in particular, It is 0.001-5 mass parts with respect to 100 mass parts of polyvinyl acetals, Preferably it is the range of 0.01-1 mass part. When the amount of the antioxidant is less than 0.001 part by mass, a sufficient effect may not be exhibited, and when it exceeds 5 parts by mass, the effect cannot be improved by increasing the blending amount.

  Examples of the method for producing PVA used in the method 2) include the following A) to H).

  A) A vinyl ester monomer from which a radical polymerization inhibitor contained in the raw vinyl ester monomer has been removed in advance is used for the polymerization.

  B) A vinyl ester monomer having a total content of impurities contained in the raw material vinyl ester monomer of preferably 1 to 1200 ppm, more preferably 3 to 1100 ppm, and still more preferably 5 to 1000 ppm is used for radical polymerization. Impurities include aldehydes such as acetaldehyde, crotonaldehyde, and acrolein; acetals such as acetaldehyde dimethyl acetal, crotonaldehyde dimethyl acetal, and acrolein dimethyl acetal obtained by acetalizing the aldehyde with a solvent alcohol; ketones such as acetone; methyl acetate and ethyl acetate And esters.

  C) In order to suppress the alcoholysis and hydrolysis of the monomer by alcohol and a small amount of water in a series of steps of radical polymerization of the raw material vinyl ester monomer in an alcohol solvent and collecting and reusing unreacted monomer, Organic acids, specifically hydroxycarboxylic acids such as glycolic acid, glyceric acid, malic acid, citric acid, lactic acid, tartaric acid, salicylic acid; malonic acid, succinic acid, maleic acid, phthalic acid, oxalic acid, glutaric acid, etc. A carboxylic acid or the like is added to suppress the generation of aldehydes such as acetaldehyde generated by decomposition as much as possible. The addition amount of the organic acid is preferably 1 to 500 ppm, more preferably 3 to 300 ppm, and still more preferably 5 to 100 ppm with respect to the raw material vinyl ester monomer.

  D) As a solvent used for polymerization, a solvent having a total content of impurities of preferably 1 to 1200 ppm, more preferably 3 to 1100 ppm, and still more preferably 5 to 1000 ppm. Examples of the impurities contained in the solvent include those described above as the impurities contained in the raw material vinyl ester monomer.

  E) When the vinyl ester monomer is radically polymerized, the ratio of the solvent to the vinyl ester monomer is increased.

  F) An organic peroxide is used as a radical polymerization initiator used for radical polymerization of a vinyl ester monomer. Organic peroxides include acetyl peroxide, isobutyl peroxide, diisopropyl peroxycarbonate, diallyl peroxydicarbonate, di-n-propyl peroxydicarbonate, dimyristyl peroxydicarbonate, and di (2-ethoxyethyl) peroxide. Examples include oxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (methoxyisopropyl) peroxydicarbonate, and di (4-tert-butylcyclohexyl) peroxydicarbonate. It is preferable to use peroxydicarbonate with a period of 10 to 110 minutes.

  G) When an inhibitor is added after radical polymerization of the vinyl ester monomer to suppress polymerization, an inhibitor of 5 molar equivalents or less is added to the remaining undecomposed radical polymerization initiator. Examples of the inhibitor include a compound having a conjugated double bond having a molecular weight of 1000 or less and a compound that stabilizes a radical and inhibits a polymerization reaction. Specifically, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 1,3-pentadiene, 2 , 3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, 2-methyl-1 , 3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4-hexadiene, , 3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene, 1-ethoxy-1,3- Tadiene, 2-ethoxy-1,3-butadiene, 2-nitro-1,3-butadiene, chloroprene, 1-chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 2-bromo-1, Conjugated dienes composed of a conjugated structure of two carbon-carbon double bonds such as 3-butadiene, fulvene, tropone, osymene, ferrandrene, myrcene, farnesene, semblene, sorbic acid, sorbic acid ester, sorbic acid salt, and abietic acid; 1,3,5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, conjugated triene having a conjugated structure of three carbon-carbon double bonds such as cholecalciferol Carbons such as cyclooctatetraene, 2,4,6,8-decatetraene-1-carboxylic acid, retinol, retinoic acid, etc. Polyenes such as conjugated polyene consisting Motoni double bond of four or more conjugated structure. Any one having a plurality of stereoisomers such as 1,3-pentadiene, myrcene, and farnesene may be used. Furthermore, p-benzoquinone, hydroquinone, hydroquinone monomethyl ether, 2-phenyl-1-propene, 2-phenyl-1-butene, 2,4-diphenyl-4-methyl-1-pentene, 3,5-diphenyl-5 Methyl-2-heptene, 2,4,6-triphenyl-4,6-dimethyl-1-heptene, 3,5,7-triphenyl-5-ethyl-7-methyl-2-nonene, 1,3- Diphenyl-1-butene, 2,4-diphenyl-4-methyl-2-pentene, 3,5-diphenyl-5-methyl-3-heptene, 1,3,5-triphenyl-1-hexene, 2,4 , 6-triphenyl-4,6-dimethyl-2-heptene, 3,5,7-triphenyl-5-ethyl-7-methyl-3-nonene, 1-phenyl-1,3-butadiene, 1,4 - Aromatic compounds such as Eniru 1,3-butadiene.

  H) An alcohol solution of polyvinyl ester from which the remaining vinyl ester monomer is removed as much as possible is used for the saponification reaction. Preferably, the residual monomer removal rate is 99% or more, more preferably 99.5% or more, still more preferably 99.8% or more.

  A desired PVA can be obtained by appropriately combining A) to H). The polyvinyl acetal obtained by acetalizing the PVA thus obtained is preferably used as a raw material for the interlayer film for laminated glass.

  As the light diffusing fine particles contained in the interlayer film for laminated glass of the present invention, a composition obtained by removing the light diffusing fine particles from the composition constituting the interlayer film for laminated glass of the present invention (hereinafter referred to as intermediate for laminated glass). Either or both of inorganic light diffusing fine particles and organic light diffusing fine particles having a large absolute difference between the refractive index of the film base) and the refractive index of the light diffusing fine particles are used. The difference absolute value of the refractive index between the light diffusing fine particles and the interlayer film base material for laminated glass is 0.20 or more, more preferably 0.40 or more, and further preferably 0.60 or more. . When the difference absolute value is less than 0.20, the irradiated light may not be sufficiently diffused. Further, the upper limit of the absolute difference in refractive index between the light diffusing fine particles and the interlayer film base material for laminated glass is not particularly limited, but from the viewpoint of reducing the haze of the obtained laminated glass, it is 3.0 or less. It is preferable that it is, and it is more preferable that it is 2.0 or less.

  Examples of the inorganic light diffusing fine particles include metal oxides such as calcium sulfate, barium sulfate, titanium oxide, aluminum oxide, magnesium oxide, and zinc oxide; aluminum hydroxide, silica, glass, talc, mica, white carbon, etc. These may be those that have been surface treated with fatty acids or the like. Examples of the organic light diffusing fine particles include acrylic polymer particles, styrene polymer particles, silicone polymer particles, and fluorine polymer particles. Of these light diffusing fine particles, inorganic light diffusing fine particles are preferable, metal oxides are more preferable, titanium oxide or zinc oxide is further preferable, and titanium oxide is particularly preferable. Moreover, these may be used independently and may use 2 or more types together.

  The average particle diameter of the light diffusing fine particles is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 2 μm or less. When the average particle diameter exceeds 10 μm, the light diffusing fine particles can be visually confirmed, and the appearance is poor. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.20 μm or more, more preferably 0.25 μm or more from the viewpoint of light diffusibility. The shape of the light diffusing fine particles is not particularly limited, and examples thereof include a true sphere, a sphere, an ellipse, a column, a weight, a plate, a needle, a star, a hollow, and an indefinite shape. Here, in this specification, an average particle diameter points out the volume reference | standard average diameter measured by the laser diffraction type particle size distribution measuring method.

  The content of the light diffusing fine particles is preferably in the range of 0.001 to 0.040 mass% in the composition constituting the interlayer film for laminated glass, and is in the range of 0.002 to 0.030 mass%. More preferably, it is more preferable that it is the range of 0.003-0.025 mass%, and it is especially preferable that it is the range of 0.004-0.020 mass%. When the content of the light diffusing fine particles is less than 0.001% by mass in the composition constituting the interlayer film for laminated glass, the light diffusibility of the laminated glass using the interlayer film may not be sufficient. On the other hand, when the content of the light diffusing fine particles is more than 0.040% by mass in the composition constituting the interlayer film for laminated glass, the transparency of the laminated glass using the interlayer film may not be sufficient.

  The interlayer film for laminated glass of the present invention preferably contains a plasticizer. The plasticizer is not particularly limited as long as the effect of the present invention is not impaired and there is no problem in compatibility with polyvinyl acetal. As the plasticizer, a mono- or diester of an oligoalkylene glycol having a hydroxyl group at both ends and a carboxylic acid, a diester of a dicarboxylic acid and a hydroxyl group-containing compound, or the like can be used. These can be used alone or in combination of two or more. Examples of the oligoalkylene glycol having hydroxyl groups at both ends include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,2-propylene glycol dimer and trimer, 1,3 -Propylene glycol, 1,3-propylene glycol dimer and trimer, 1,2-butylene glycol, 1,2-butylene glycol dimer and trimer, 1,4-butylene glycol, 1, 4-butylene glycol dimer and trimer, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, 1,8-octane Diol, 1,9-nonanediol, 2-methyl-1,8-octanediol, , 2-decanediol, 1,4-cyclohexane diol. Examples of the carboxylic acid include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid and decanoic acid. Here, the combination of oligoalkylene glycol and carboxylic acid is arbitrary. Among these, monoethylene and diester of triethylene glycol and 2-ethylhexanoic acid are preferable from the viewpoint of handleability (volatility during molding). Dicarboxylic acids include alkylene dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and sebacic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. An acid etc. are mentioned. Examples of the hydroxyl group-containing compound include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, nonaol, decanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, Examples include 2-butoxyethanol and the like, and diesters with the above dicarboxylic acid compounds. Here, the combination of dicarboxylic acid and a hydroxyl-containing compound is arbitrary.

  The content of the plasticizer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 10 to 100 parts by mass, more preferably 15 to 90 parts by mass with respect to 100 parts by mass of polyvinyl acetal. More preferably, it is 20-80 mass parts. When content of a plasticizer is less than 10 mass parts, there exists a possibility that desired softness | flexibility may not be obtained as an intermediate film for laminated glasses. If the content exceeds 100 parts by mass, the desired mechanical properties, in particular the penetration resistance of the laminated glass, may be reduced.

  The interlayer film for laminated glass of the present invention may contain a dispersant for the purpose of dispersing the light diffusing fine particles as long as it does not contradict the gist of the present invention. Examples of the dispersant include a phosphoric acid ester compound, a sulfuric acid ester compound, a polycarboxylic acid ester compound, and a ricinoleic acid ester compound.

  The interlayer film for laminated glass of the present invention may contain an ultraviolet absorber, an adhesion adjusting agent, a pigment, a dye, and other conventionally known additives as long as it does not contradict the gist of the present invention. Such additives will be described below.

  Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3,5-bis (α, α′-dimethylbenzyl) phenyl) -2H-benzotriazole. 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 , 5-di-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′- Benzotriazole ultraviolet absorbers such as hydroxy-5′-t-octylphenyl) benzotriazole; 2,2,6,6-tetramethyl-4-piperi Dibenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-dit -Butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3- ( Hindered amine ultraviolet absorbers such as 3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6-tetramethylpiperidine; 2,4-di-t-butylphenyl-3 , 5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and other benzoate UV absorbers; malonic acid [(4-metho Shifeniru) - methylene] - malonic acid ester ultraviolet absorbers such as dimethyl ester; 2-ethyl-2'-ethoxy - such as oxalic acid anilide-based ultraviolet absorbers such oxalanilide like. These ultraviolet absorbers can be used alone or in combination of two or more. Although there is no restriction | limiting in particular in content of the ultraviolet absorber in the intermediate film for laminated glasses, It is preferable that it is 10-50,000 ppm, and it is more preferable that it is the range of 100-10,000 ppm. If the content is less than 10 ppm, a sufficient effect may not be exhibited, and even if the content is more than 50,000 ppm, the effect cannot be improved by increasing the content.

  The interlayer film for laminated glass of the present invention may contain an adhesion adjusting agent in order to appropriately adjust the adhesion with glass. A conventionally well-known thing can be used as an adhesive control agent. For example, sodium salts, potassium salts, magnesium salts of organic acids such as acetic acid, propionic acid, butanoic acid, hexanoic acid, 2-ethylbutanoic acid and 2-ethylhexanoic acid are used. These can be used alone or in combination of two or more. The preferred content of the adhesion adjusting agent varies depending on the type, but the adhesive strength of the interlayer film for laminated glass obtained to the glass is determined by the Pummel test (described in International Publication No. 03/033583 etc.). Generally, it is preferable to adjust so that it may become 3-10. In particular, when high penetration resistance is required, it is preferable to adjust the content to be 3 to 6, and when high anti-scattering property is required, the content is adjusted to be 7 to 10. It is preferable. When high glass scattering prevention property is required, it is also a useful method not to add an adhesion modifier. Usually, the content of the adhesion adjusting agent in the interlayer film for laminated glass is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.1% by mass, and 0.001 to 0%. 0.03 mass% is more preferable.

  Moreover, a silane coupling agent is mentioned as another additive for adjusting the said adhesiveness. As for content of the silane coupling agent in the intermediate film for laminated glasses, 0.01-5 mass% is preferable.

  The glass transition temperature of the interlayer film for laminated glass of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but is preferably in the range of 0 to 50 ° C, more preferably 0 to 45 ° C. Preferably, it is 0-40 degreeC.

  The thickness of the interlayer film for laminated glass of the present invention is not particularly limited, but is preferably 0.05 to 5.0 mm, and more preferably 0.1 to 2.0 mm.

  The method for producing the interlayer film for laminated glass of the present invention is not particularly limited, but after PVA is acetalized to obtain polyvinyl acetal, the polyvinyl acetal is mixed with light diffusing fine particles and, if necessary, a plasticizer and other components. A method of melt-molding the obtained composition is preferred. As the melt molding method, a method of melt-kneading the obtained polyvinyl acetal, light diffusing fine particles, plasticizer, and other components using an extruder to form a film is preferable. The method for dispersing the light diffusing fine particles in the interlayer film for laminated glass of the present invention is not particularly limited, but a method of adding a dispersion obtained by dispersing the light diffusing fine particles in a plasticizer to the polyvinyl acetal resin is preferable. Further, the dispersion may contain a dispersant as required. The method for dispersing the light diffusing fine particles in the plasticizer is not particularly limited, but a composition in which the light diffusing fine particles, the plasticizer and other components are mixed is mixed with a bead mill, ball mill, sand mill, homogenizer, attritor, high speed rotation. The dispersion treatment can be performed by an apparatus such as an agitator or an ultrasonic dispersion apparatus. The resin temperature during extrusion is preferably 150 to 250 ° C, more preferably 170 to 230 ° C. When the resin temperature becomes too high, polyvinyl acetal is decomposed, and the content of volatile substances in the intermediate film after film formation increases. On the other hand, if the temperature is too low, the removal of volatile matter in the extruder becomes insufficient, and the content of volatile substances in the intermediate film after film formation increases. In order to efficiently remove the volatile substance, it is preferable to remove the volatile substance from the vent port by reducing the pressure in the extruder. The interlayer film for laminated glass of the present invention can also be obtained by forming a film obtained by dissolving or dispersing polyvinyl acetal, light diffusing fine particles, plasticizer and other components in an organic solvent, and then distilling off the organic solvent. Can be manufactured.

  The shape of the surface of the interlayer film for laminated glass is not particularly limited. However, in consideration of the handleability (foaming property) when laminating with glass, the melt fracture and embossing are performed on the surface in contact with the glass by a conventionally known method. It is preferable that a concavo-convex structure such as is formed. Although there is no restriction | limiting in particular about emboss height, It is preferable that they are 5 micrometers-500 micrometers, It is more preferable that they are 7 micrometers-300 micrometers, It is still more preferable that they are 10 micrometers-200 micrometers. When the emboss height is less than 5 μm, bubbles formed between the glass and the intermediate film may not be efficiently removed during lamination, and when it exceeds 500 μm, it is difficult to form the emboss. Embossing may be performed on one side of the intermediate film or on both sides, but it is usually preferable to apply it on both sides. The emboss pattern may be regular or irregular.

  In order to form such embossing, a conventionally known embossing roll method, profile extrusion method, extrusion lip embossing method using a melt fracture, or the like is employed. In particular, the embossing roll method is suitable for stably obtaining an interlayer film for laminated glass on which uniform and fine irregularities are formed.

  The embossing roll used in the embossing roll method can be produced by, for example, using an engraving mill (mother mill) having a desired concavo-convex pattern and transferring the concavo-convex pattern onto the surface of the metal roll. Moreover, an embossing roll can also be produced using laser etching. Further, after forming a fine concavo-convex pattern on the roll surface as described above, the surface is blasted with an abrasive such as aluminum oxide, silicon oxide, glass beads, etc. to form a finer concavo-convex pattern. You can also.

  Moreover, it is preferable to perform a mold release treatment on the embossing roll used in the embossing roll method. When a roll that has not been subjected to release treatment is used, troubles in which the interlayer film for laminated glass cannot be peeled off from the roll tend to occur. For the release treatment, a known method such as silicone treatment, Teflon (registered trademark) treatment, plasma treatment or the like can be used.

  In the present invention, as a polyvinyl acetal that is a raw material for the interlayer film for laminated glass, a film may be formed using only a virgin resin (one that does not contain recycled polyvinyl acetal). The film may be reused. Usually, for film formation, a film forming apparatus provided with a weighing machine such as a gear pump and a die such as a T die in an extruder is used. Generally, when forming an interlayer film for laminated glass or the like, both ends (trims) of the interlayer film for laminated glass and the like are cut off. It is very important to collect and reuse such trims from the viewpoints of energy saving, effective utilization of resources and improvement of yield. Further, off-spec products produced during the production of an interlayer film for laminated glass having irregularities on the surface are also useful because they can be reused in the same manner as the trim. The interlayer film for laminated glass of the present invention has few foreign matters (undissolved content) generated when the film is formed by melting. Further, since the interlayer film for laminated glass of the present invention is less colored when heat-treated, the recovered interlayer film for laminated glass (trim, off-spec intermediate film for laminated glass) can be effectively reused. As a method of charging the recovered laminated glass interlayer into the extruder again, a method in which the trim or off-spec intermediate film for laminated glass wound on a roll is unwound as it is and re-entered into the extruder; Examples include a method in which an intermediate film for laminated glass of an off-spec product wound on a roll is cut into a certain size and then re-entered into an extruder. When the intermediate film for laminated glass of the present invention is formed, the ratio of the virgin resin in the raw material to the intermediate film for recovered laminated glass (virgin resin: intermediate film for recovered laminated glass) is between 0: 100 and 100: 0. Can be changed arbitrarily.

  In the case of producing a laminated glass interlayer film by reusing the trim or off-spec laminated glass interlayer film, the content of the light diffusing fine particles, the plasticizer, and other components can be adjusted by the following method. A desired interlayer film for laminated glass is obtained by adjusting the amount of each component added to the extruder while analyzing the components of the interlayer film for laminated glass obtained.

  A laminated glass formed by bonding a plurality of glass plates using the interlayer film for laminated glass is a preferred embodiment of the present invention. The laminated glass can be produced by sandwiching the intermediate film between at least two glass plates and heating and bonding the intermediate film. The glass used for the laminated glass is not particularly limited. In addition to inorganic glass such as float plate glass, tempered plate glass, polished plate glass, mold plate glass, netted plate glass, heat ray absorbing plate glass, conventionally known polymethyl methacrylate, polycarbonate and the like. Organic glass or the like can be used. These may be either colorless or colored. From the viewpoint of transparency when using laminated glass, these glasses preferably have a haze of 20% or less measured by a method based on JIS K 7105. Further, the same type of glass may be laminated, or different types of glass may be laminated. Although the thickness of glass is not specifically limited, It is preferable that it is 100 mm or less. Moreover, there is no restriction | limiting in particular about the shape of the said glass, Even if it is glass with curvature, such as a simple flat plate glass, the sunroof glass for motor vehicles.

  The interlayer film for laminated glass of the present invention has a haze of 20% or less by a method based on JIS K 7105 from the viewpoint of transparency when sandwiched between two 3 mm thick glass plates to form a laminated glass. Yes, it is more preferably 17.5% or less, and further preferably 15% or less. The lower limit of haze is not particularly limited, but is preferably 3% or more. If the lower limit is less than 3%, the irradiated light may not be sufficiently diffused. The glass plate used in the measurement usually has a haze of 20% or less by itself.

  The laminated glass can be produced by a conventionally known method, and examples thereof include a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. Further, there is a method in which the obtained laminate is put into an autoclave after being temporarily pressed using these methods.

When using a vacuum laminator, for example, the glass and the interlayer film are laminated at 100 to 200 ° C., particularly 130 to 160 ° C. under a reduced pressure of 1 × 10 ^{−6 to} 3 × 10 ⁻² MPa. A method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683, and is laminated at 130 to 145 ° C. under a pressure of about 2 × 10 ⁻² MPa.

  As a production method using a nip roll, there is a method in which after degassing with a roll at a temperature not higher than the flow start temperature of the interlayer film for laminated glass, pressure bonding is further performed at a temperature close to the flow start temperature. Specifically, for example, a method of heating to 30 to 70 ° C. with an infrared heater or the like, then degassing with a roll, and further heating to 50 to 120 ° C. followed by pressure bonding with the roll can be mentioned.

  When pressure bonding is performed using the above-described method, and then further pressure bonding is performed, the operating conditions of the autoclave process are appropriately selected depending on the thickness and configuration of the laminated glass, for example, 1.0 to 1.5 MPa It is preferable to process at 130-145 degreeC under a pressure for 0.5 to 3 hours.

  The laminated glass of the present invention obtained by the above method is excellent in penetration resistance, transparency and light diffusibility, and therefore can be used as a light diffusing plate. For example, as a light-shielding plate that also serves as a window material that uses transparency when the light source is turned off and becomes opaque due to diffused light in the surface direction when the light source is turned on, as a light emitting plate for lighting, decorative plates, signboards, signs, etc. It can be suitably used for interior materials, members for transportation equipment such as automobiles and airplanes, members for electrical equipment, and members for electronic equipment.

  When the laminated glass of the present invention is used as the transportation equipment member, a specific example of application includes a sunroof panel. A sunroof is an opening provided in a transport device, particularly an automobile roof. A sunroof panel, which is a part of the sunroof, is made of a translucent material and serves as a daylighting unit. When the laminated glass of the present invention is used as a sunroof panel, it is excellent in design while ensuring safety.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, “%” and “part” mean “% by mass” and “part by mass” unless otherwise specified.

[GPC measurement]
(measuring device)
GPC measurement was performed using “GPCmax” manufactured by VISCOTECH. As a differential refractive index detector, “TDA305” manufactured by VISCOTECH was used. “UV Detector 2600” manufactured by VISCOTECH was used as an ultraviolet-visible absorption detector. The optical path length of the detection cell of the absorptiometric detector is 10 mm. “GPC HFIP-806M” manufactured by Showa Denko KK was used for the GPC column. Moreover, OmniSEC (Version 4.7.0.406) attached to the apparatus was used as analysis software.

(Measurement condition)
The sample was dissolved in HFIP containing 20 mmol / l sodium trifluoroacetate to prepare a solution (concentration 1.00 mg / ml) in which the sample was dissolved. The supernatant of the solution was taken, filtered through a 0.45 μm polytetrafluoroethylene filter, and used for measurement.

  As the mobile phase, HFIP containing 20 mmol / l sodium trifluoroacetate was used. The mobile phase flow rate was 1.0 ml / min. The sample injection amount was 100 μl, and measurement was performed at a GPC column temperature of 40 ° C.

In addition, the sample in which the PVA viscosity average polymerization degree in a sample exceeded 2400 performed GPC measurement using the sample (100 microliters) diluted suitably. The absorbance at a sample concentration of 1.00 mg / ml was calculated from the measured value according to the following formula. α (mg / ml) is the concentration of the diluted sample.
Absorbance at a sample concentration of 1.00 mg / ml = (1.00 / α) × measured value of absorbance

(Create a calibration curve)
As a standard, monodispersed PMMA (peak top molecular weight: 1944000, 790000, 467400, 271400, 144000, 79250, 35300, 13300, 7100, 1960, 1020, 690) manufactured by Agilent Technologies was measured, and a differential refractive index detector. A calibration curve for converting the elution volume into the PMMA molecular weight was prepared for each of the absorptiometric detectors. The analytical software was used to create each calibration curve. In this measurement, a column in a state where the peaks of standard samples having both molecular weights of 1944000 and 271400 can be separated in the PMMA measurement is used.

  In this device, the signal intensity obtained from the differential refractive index detector is expressed in millivolts, and the signal intensity obtained from the absorptiometric detector is expressed in absorbance (absunit: Absorbance unit).

[Synthesis of polyvinyl acetate]
PVAc-1
A 6L separable flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux tube was deoxygenated in advance, and vinyl acetate monomer (VAM) 2555 g containing 500 ppm of acetaldehyde (AA) and 50 ppm of acetaldehyde dimethyl acetal (DMA). 945 g of methanol (MeOH) containing 50 ppm of acetaldehyde dimethyl acetal and acetaldehyde content of less than 1 ppm; 1% methanol solution of tartaric acid in an amount of 20 ppm of tartaric acid in VAM was charged. While blowing nitrogen into the flask, the temperature inside the flask was adjusted to 60 ° C. In addition, -10 degreeC ethylene glycol / water solution was circulated through the reflux pipe. A 0.55 mass% methanol solution of di-n-propyl peroxydicarbonate was prepared, and 18.6 mL was added into the flask to initiate polymerization. The amount of di-n-propyl peroxydicarbonate added at this time was 0.081 g. A methanol solution of di-n-propyl peroxydicarbonate was sequentially added at a rate of 20.9 mL / hour until the completion of polymerization. During the polymerization, the temperature in the flask was kept at 60 ° C. Four hours after the start of polymerization, when the solid content concentration of the polymerization solution reached 25.1%, 0.0141 g of sorbic acid (3% of di-n-propyl peroxydicarbonate remaining undecomposed in the polymerization solution) was obtained. After adding 1200 g of contained methanol (corresponding to a molar equivalent), the polymerization solution was cooled to stop the polymerization. When the polymerization was stopped, the polymerization rate of VAM was 35.0%. After the polymerization solution was cooled to room temperature, the inside of the flask was decompressed using a water aspirator to distill off VAM and methanol, thereby precipitating polyvinyl acetate. After 3000 g of methanol was added to the precipitated polyvinyl acetate and the polyvinyl acetate was dissolved while heating at 30 ° C., the pressure in the flask was reduced again using a water aspirator to distill off VAM and methanol. Polyvinyl acetate was precipitated. The operation of dissolving polyvinyl acetate in methanol and then precipitating it was further repeated twice. Methanol was added to the precipitated polyvinyl acetate to obtain a 40% by mass methanol solution of polyvinyl acetate (PVAc-1) with a VAM removal rate of 99.8%.

  The polymerization degree was measured using a part of the methanol solution of PVAc-1 obtained. To a methanol solution of PVAc-1, a 10% methanol solution of sodium hydroxide was added so that the molar ratio of sodium hydroxide to vinyl acetate units in polyvinyl acetate was 0.1. When the gelled product was formed, the gel was pulverized and subjected to Soxhlet extraction with methanol for 3 days. The obtained polyvinyl alcohol was dried and the viscosity average polymerization degree was measured. The degree of polymerization was 1700.

PVAc-2-13
Except having changed into the conditions described in Table 1, polyvinyl acetate (PVAc-2-13) was obtained by the same method as PVAc-1. In Table 1, “ND” means less than 1 ppm. The polymerization degree of each obtained polyvinyl acetate was calculated | required similarly to PVAc-1. The results are shown in Table 1.

[Synthesis and Evaluation of PVA]
PVA-1
Water with respect to vinyl acetate monomer units in methanol and polyvinyl acetate so that the total solid concentration (saponification concentration) is 30% by mass with respect to a 40% by mass methanol solution of polyvinyl acetate of PVAc-1. An 8% methanol solution of sodium hydroxide was added with stirring so that the molar ratio of sodium oxide was 0.020, and the saponification reaction was started at 40 ° C. The gel is pulverized when the gelated product is generated as the saponification reaction proceeds, and the crushed gel is transferred to a container at 40 ° C. When 60 minutes have elapsed from the start of the saponification reaction, methanol / methyl acetate / water ( 25/70/5 mass ratio) solution and neutralized. The obtained swollen gel was centrifuged, and methanol twice as much as the swollen gel was added, immersed, left for 30 minutes, and then centrifuged four times, 60 ° C. for 1 hour, 100 It dried at 2 degreeC for 2 hours, and PVA-1 was obtained.

  The polymerization degree and saponification degree of PVA-1 were determined by the method described in JIS K 6726. The degree of polymerization was 1700, and the degree of saponification was 99.1 mol%. These physical property data are shown in Table 2.

  After ashing PVA-1, the sodium acetate content of PVA-1 was calculated | required by measuring the amount of sodium in the obtained ash using the ICP emission-analysis apparatus "IRISAP" by Jarrel Ash. . The sodium acetate content was 0.7% (0.20% in terms of sodium). These physical property data are shown in Table 2.

PVA-2, 3 and comparative PVA-1 to 3
Each PVA was synthesize | combined like PVA-1 except having changed into the conditions shown in Table 2. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 2.

PVA-4, comparative PVA-4, 5
Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 3 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 3.

PVA-5, comparative PVA-6-8
Each PVA was synthesized in the same manner as PVA-1 except that the conditions shown in Table 4 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 4.

PVA-6-8, comparative PVA-9-11
Each PVA was synthesized in the same manner as PVA-1 except that the conditions shown in Table 5 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 5.

PVA-9, comparative PVA-12, 13
Each PVA was synthesized in the same manner as PVA-1 except that the conditions shown in Table 6 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 6.

PVA-10, comparative PVA-14, 15
Each PVA was synthesized in the same manner as PVA-1, except that the conditions were changed to those shown in Table 7. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 7.

[Synthesis and Evaluation of PVB]
PVB-1
A 10 L glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion exchange water and 660 g of PVA-1 (PVA concentration 7.5%), and the contents were heated to 95 ° C. The PVA was completely dissolved. Next, the contents are gradually cooled to 10 ° C. over about 30 minutes while stirring at 120 rpm, and then 384 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 150 minutes. It was. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, the resin was rewashed with ion-exchanged water and then dried to obtain PVB-1.

(Composition of PVB)
The degree of butyralization (degree of acetalization) of PVB-1, the content of vinyl acetate monomer units, and the content of vinyl alcohol monomer units were measured according to JIS K 6728. The degree of butyralization (degree of acetalization) was 68.2 mol%, the content of vinyl acetate monomer units was 0.9 mol%, and the content of vinyl alcohol monomer units was 30.9 mol%. It was. The results are shown in Table 8.

PVB-2, 3 and comparative PVB-1, 2
PVB was synthesized and evaluated in the same manner as PVB-1, except that the raw material PVA was changed to that shown in Table 8. The results are shown in Table 8.

PVB-4
PVB was synthesized and evaluated in the same manner as PVB-1, except that the amount of n-butyraldehyde added was changed to 365 g. The results are shown in Table 8. The degree of butyralization (degree of acetalization) of PVB is 64.3 mol%, the content of vinyl acetate monomer units is 0.9 mol%, and the content of vinyl alcohol monomer units is 34.8. Mol%.

PVB-5
PVB was synthesized and evaluated in the same manner as PVB-1, except that the amount of n-butyraldehyde added was changed to 449 g. The results are shown in Table 8. The degree of butyralization (degree of acetalization) of PVB is 79.8 mol%, the content of vinyl acetate monomer units is 0.9 mol%, and the content of vinyl alcohol monomer units is 19.3. Mol%.

Comparative PVB-3
PVB was synthesized and evaluated in the same manner as PVB-1, except that the amount of n-butyraldehyde added was changed to 271 g. The results are shown in Table 8. The degree of butyralization (degree of acetalization) of PVB was 48.2 mol%, the content of vinyl acetate monomer units was 0.9 mol%, and the content of vinyl alcohol monomer units was 50.9. Mol%.

Comparative PVB-4
A 10 L glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion exchange water and 660 g of PVA-1 (PVA concentration 7.5%), and the contents were heated to 95 ° C. The PVA was completely dissolved. Next, the contents are gradually cooled to 10 ° C. over about 30 minutes while stirring at 120 rpm, and then 740 g of n-butyraldehyde and 810 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 150 minutes. It was. Thereafter, the temperature was raised to 80 ° C. over 90 minutes, kept at 80 ° C. for 16 hours, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, the resin was rewashed with ion-exchanged water and dried to obtain PVB. PVB obtained in the same manner as PVB-1 was evaluated. The results are shown in Table 8. The degree of butyralization (degree of acetalization) of PVB is 87.4 mol%, the content of vinyl acetate monomer units is 0.9 mol%, and the content of vinyl alcohol monomer units is 11.7. Mol%.

Comparative PVB-5
A 10L glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of comparative PVA-3 (PVA concentration 5.0%), and the contents were raised to 95 ° C. Warm to completely dissolve the PVA. Next, the contents were gradually cooled to 8 ° C. over about 30 minutes while stirring at 120 rpm, and then 384 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to the vessel, and a butyralization reaction was performed for 150 minutes. It was. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, PVB was obtained by washing again with ion-exchanged water and drying. PVB obtained in the same manner as PVB-1 was evaluated. The results are shown in Table 8. The degree of butyralization (degree of acetalization) of PVB was 68.5 mol%, the content of vinyl acetate monomer units was 1.5 mol%, and the content of vinyl alcohol monomer units was 30.0. Mol%.

PVB-6
Into a 10 L glass container equipped with a reflux condenser, thermometer and squid type stirring blade, 8234 g of ion-exchanged water and 526 g of PVA-4 were charged (PVA concentration 6.0%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents are gradually cooled to 15 ° C. over about 30 minutes while stirring at 120 rpm, and then 307 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 120 minutes. It was. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, PVB was obtained by washing again with ion-exchanged water and drying. PVB obtained in the same manner as PVB-1 was evaluated. The results are shown in Table 9. The PVB obtained had a butyralization degree (acetalization degree) of 68.2 mol%, a vinyl acetate monomer unit content of 1.3 mol%, and a vinyl alcohol monomer unit content of It was 30.5 mol%.

Comparative PVB-6, 7
PVB was synthesized and evaluated in the same manner as PVB-6, except that the raw material PVA was changed to that shown in Table 9. The results are shown in Table 9.

PVB-7
A 10 L glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8322 g of ion-exchanged water and 438 g of PVA-5 (PVA concentration 5.0%), and the contents were heated to 95 ° C. Thus, the PVA was completely dissolved. Next, the contents are gradually cooled to 20 ° C. over about 30 minutes while stirring at 120 rpm, and then 256 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 120 minutes. It was. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, PVB was obtained by re-washing with ion-exchanged water and drying. PVB obtained in the same manner as PVB-1 was evaluated. The results are shown in Table 10. The obtained PVB had a butyralization degree (acetalization degree) of 68.1 mol%, a vinyl acetate monomer unit content of 1.5 mol%, and a vinyl alcohol monomer unit content of It was 30.4 mol%.

Comparative PVB-8-10
Except having changed raw material PVA into what is shown in Table 10, synthesis and evaluation of PVB were implemented like PVB-7. The results are shown in Table 10.

PVB-8
A 10L glass container equipped with a reflux condenser, thermometer, and squid type stirring blades was charged with 8100 g of ion-exchanged water and 660 g of PVA-6 (PVA concentration 7.5%), and the contents were heated to 95 ° C. And completely dissolved. Next, the contents are gradually cooled to 15 ° C. over about 30 minutes while stirring at 120 rpm. Then, 432 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 90 minutes. It was. Thereafter, the temperature was raised to 45 ° C. over 30 minutes, held at 45 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral. PVB obtained in the same manner as PVB-1 was evaluated. The results are shown in Table 11. The obtained PVB had a butyralization degree (acetalization degree) of 74.1 mol%, a vinyl acetate monomer unit content of 8.1 mol%, and a vinyl alcohol monomer unit content of It was 17.8 mol%.

PVB-9, 10
Except having changed raw material PVA into what is shown in Table 11, synthesis and evaluation of PVB were implemented like PVB-8. The results are shown in Table 11.

PVB-11
PVB was synthesized and evaluated in the same manner as PVB-8 except that the amount of n-butyraldehyde added was changed to 307 g. The results are shown in Table 11. The PVB obtained had a butyralization degree (acetalization degree) of 63.2 mol%, a vinyl acetate monomer unit content of 8.5 mol%, and a vinyl alcohol monomer unit content of It was 28.3 mol%.

PVB-12
PVB was synthesized and evaluated in the same manner as PVB-8 except that the amount of n-butyraldehyde added was changed to 458 g. The results are shown in Table 11. The obtained PVB had a butyralization degree (acetalization degree) of 78.5 mol%, a vinyl acetate monomer unit content of 7.5 mol%, and a vinyl alcohol monomer unit content of It was 14.0 mol%.

Comparative PVB-11, 12
Except having changed raw material PVA into what is shown in Table 11, synthesis and evaluation of PVB were implemented like PVB-8. The results are shown in Table 11.

Comparative PVB-13
A 10 L glass container equipped with a reflux condenser, thermometer, and squid-type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of comparative PVA-11 (PVA concentration 7.5%), and the contents were raised to 95 ° C. Warm to completely dissolve the PVA. Next, the contents were gradually cooled to 10 ° C. over about 60 minutes while stirring at 120 rpm, and then 450 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to the vessel, and a butyralization reaction was performed for 90 minutes. It was. Thereafter, the temperature was raised to 30 ° C. over 30 minutes, held at 30 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, PVB was obtained by washing again with ion-exchanged water and drying. PVB obtained in the same manner as PVB-1 was evaluated. The results are shown in Table 11. The obtained PVB had a butyralization degree (acetalization degree) of 74.3 mol%, a vinyl acetate monomer unit content of 7.9 mol%, and a vinyl alcohol monomer unit content of It was 17.8 mol%.

PVB-13
A 10L glass vessel equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8234 g of ion-exchanged water and 526 g of PVA-9 (PVA concentration 6.0%), and the contents were heated to 95 ° C. Thus, the PVA was completely dissolved. Next, the contents are gradually cooled to 15 ° C. over about 60 minutes while stirring at 120 rpm, and then 344 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 90 minutes. It was. Thereafter, the temperature was raised to 45 ° C. over 30 minutes, held at 45 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, PVB was obtained by washing again with ion-exchanged water and drying. PVB obtained in the same manner as PVB-1 was evaluated. The results are shown in Table 12. The obtained PVB had a butyralization degree (acetalization degree) of 74.6 mol%, a vinyl acetate monomer unit content of 8.3 mol%, and a vinyl alcohol monomer unit content of It was 17.1 mol%.

Comparative PVB-14, 15
Except having changed raw material PVA into what is shown in Table 12, synthesis and evaluation of PVB were implemented like PVB-13. The results are shown in Table 12.

PVB-14
A 10L glass vessel equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8234 g of ion-exchanged water and 438 g of PVA-10 (PVA concentration 5.0%), and the contents were heated to 95 ° C. Thus, the PVA was completely dissolved. Next, the contents are gradually cooled to 15 ° C. over about 60 minutes while stirring at 120 rpm, and then 265 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 90 minutes. It was. Thereafter, the temperature was raised to 45 ° C. over 30 minutes, held at 45 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, PVB was obtained by washing again with ion-exchanged water and drying. PVB obtained in the same manner as PVB-1 was evaluated. The results are shown in Table 13. The PVB obtained had a butyralization degree (acetalization degree) of 73.2 mol%, a vinyl acetate monomer unit content of 8.1 mol%, and a vinyl alcohol monomer unit content of It was 18.7 mol%.

Comparative PVB-16, 17
PVB was synthesized and evaluated in the same manner as PVB-14 except that the raw material PVA was changed to that shown in Table 13. The results are shown in Table 13.

Example 1
(Preparation of interlayer film for laminated glass)
Titanium oxide fine particles “JR-1000” (refractive index: 2.72) 0.007 parts by mass as light diffusing fine particles, 0.014 parts by mass of magnesium acetate, and triethylene glycol di-2-ethylhexa as a plasticizer 19 parts by weight of noate was mixed and stirred for 30 minutes using a stirrer to prepare a mixed solution. The mixed solution was added to 50 parts by mass of PVB-1 powder, and melt-kneaded for 5 minutes at 160 ° C. and 50 rpm using a lab plast mill “C model” manufactured by Toyo Seiki Seisakusho. During melt kneading, nitrogen (100 mL / min) was continuously blown into the container. The obtained kneaded material was hot-pressed at 160 ° C. and 5 MPa for 30 minutes to produce an interlayer film for laminated glass having a size of 20 cm × 20 cm and a thickness of 760 μm. At this time, the interlayer film for laminated glass contains 0.0101% by mass of light diffusing fine particles. GPC measurement of the obtained interlayer film for laminated glass and evaluation of foreign matters (undissolved part) were performed as follows.

(GPC measurement)
The obtained interlayer film for laminated glass was heated by hot pressing at 230 ° C. under a pressure of 2 MPa for 3 hours, and then cooled and subjected to a heat treatment to obtain an interlayer film for laminated glass. A sample was collected from the vicinity of the center, and the obtained sample was subjected to GPC measurement by the above method.

The peak top molecular weight (A) measured by the differential refractive index detector was 95,000, and the signal intensity (a) at the peak top molecular weight (A) was 108.8 mV. The peak top molecular weight (B) measured with an absorptiometric detector (280 nm) is 44900, and the signal intensity (absorbance, b) at the peak top molecular weight (B) is 1.63 mV (1.63 × 10 ^−3). Absorbance unit). The obtained peak top molecular weight (A) and peak top molecular weight (B) are expressed by the following formula (AB) / A
The value obtained by substituting for was 0.53. The results are shown in Table 14. The molecular weight at this time is a value converted from the elution volume using a calibration curve (PMMA equivalent molecular weight).

The peak top molecular weight (C) measured with an absorptiometric detector (320 nm) determined in the same manner as the method for determining the peak top molecular weight (B) except that the measurement wavelength is different is 45600, and the peak top molecular weight The signal intensity (absorbance, c) in (C) was 1.03 mV (1.03 × 10 ⁻³ absorption unit). The peak top molecular weight (A) and the peak top molecular weight (C) are expressed by the following formula (AC) / A
The value obtained by substituting for was 0.52. The results are shown in Table 14.

  As monodisperse PMMA, American Polymer Standard Corp. “PMMA85K” (weight average molecular weight 85450, number average molecular weight 74300, intrinsic viscosity 0.309) manufactured by the company was used. The monodispersed PMMA was measured by GPC by the above method. The signal intensity (x) at the peak top molecular weight measured with a differential refractive index detector, which was determined in the same manner as the method for determining the peak top molecular weight (A), was 390.82 mV. In addition, the signal intensity (absorbance, y) at the peak top molecular weight measured with an absorptiometric detector (220 nm) obtained in the same manner as the method for determining the peak top molecular weight (B) was 269.28 mV (0.26928 absorber). Unit).

Signal intensity (a), peak top molecular weight (b), signal intensity (x), and signal intensity (y) are expressed by the following formulas (b / y) / (a / x)
The value obtained by substituting for was 2.17 × 10 ⁻² . The results are shown in Table 14.

Signal intensity (a), peak top molecular weight (c), signal intensity (x), and signal intensity (y) are represented by the following formula (c / y) / (a / x)
The value obtained by substituting for was 1.37 × 10 ⁻² . The results are shown in Table 14.

(Measurement of average particle size of light diffusing fine particles)
Using a laser diffraction / scattering particle size distribution measuring device “Partica LA-950” manufactured by HORIBA, Ltd., a mixture prepared in the same manner as the mixed liquid preparation method described in the section “Preparation of an interlayer film for laminated glass” The volume-based average diameter of the light diffusing fine particles in the liquid was measured and used as the average particle diameter of the fine particles. The evaluation results are shown in Table 14.

(Foreign matter in the interlayer film for laminated glass)
The obtained interlayer film for laminated glass is sandwiched between two transparent glass plates (vertical 20 cm × width 20 cm, thickness 3 mm), and the air between the glass plate and the interlayer film for laminated glass is extruded to 110 ° C. Pre-adhesion was performed by passing a press roll. The laminated body after the preliminary adhesion was allowed to stand at 135 ° C. and 1.2 MPa for 30 minutes in an autoclave to produce a laminated glass (20 sheets in total). The number of foreign matters in the laminated glass obtained using a magnifying glass was counted. The total number of foreign substances in 20 laminated glasses was determined and evaluated according to the following criteria. The evaluation results are shown in Table 14.
A: 0 (pieces / 20 sheets)
B: 1-2 (pieces / 20 sheets)
C: 2-5 (pieces / 20 sheets)
D: 5-11 (pieces / 20 sheets)
E: 12 or more (pieces / 20 sheets)

(Color resistance of interlayer film for laminated glass)
The same thing as the kneaded material used for preparation of the intermediate film for laminated glasses containing PVB-1 mentioned above was produced. To 34.5 parts by mass of the kneaded product, 25 parts by mass of PVB-1 powder, 0.0035 parts by mass of titanium oxide fine particles “JR-1000”, triethylene glycol di-2-ethylhexanoate, 9. 5 parts by mass and 0.007 parts by mass of magnesium acetate were mixed, and the mixture obtained by stirring for 30 minutes using a stirrer was added, and again using a lab plast mill “C model” manufactured by Toyo Seiki Seisakusho Co., Ltd., 140 ° C. For 5 minutes at 50 rpm. During melt kneading, nitrogen (100 mL / min) was continuously blown into the container. Further, repeat the operation of adding the same amount of the comparative PVB-1 powder, “Kuraray polyol P-510” and magnesium acetate to 40 parts by mass of the obtained kneaded material, and kneading under the same conditions as above. It was. Using the obtained kneaded material (repeated kneaded material-1), an interlayer film for laminated glass was produced in the same manner as the method for producing the interlayer film for laminated glass containing PVB-1. And the laminated glass was produced using the said intermediate film similarly to the production method of the laminated glass described in the term "The foreign material in the intermediate film for laminated glasses". Yellowness of the laminated glass obtained here (using PVB repeatedly heated) and the laminated glass obtained using the above “foreign matter in the interlayer film for laminated glass” (using virgin PVB) YI) was measured, and the coloration resistance was evaluated according to the following criteria from the difference in yellowness (ΔYI) between the two. The measurement was performed according to JIS K 7105 using an SM color computer “SM-TH” manufactured by Suga Test Instruments Co., Ltd.
The evaluation results are shown in Table 14.
A: Less than 0.5
B: 0.5 or more and less than 1.0 C: 1.0 or more and less than 1.8 D: 1.8 or more and less than 3.0 E: 3.0 or more

(Penetration resistance of laminated glass)
The same thing as the intermediate film for laminated glasses produced using the repetitive kneaded material-1 described in the section of “Coloring resistance of interlayer film for laminated glass” was produced. The laminated glass interlayer film is conditioned at 23 ° C. and 28% RH for 24 hours, and then sandwiched between two transparent glass plates (30 cm × 30 cm). Pre-adhesion was performed by passing a press roll at 110 ° C. while extruding the air in between. The laminated body after the preliminary adhesion was allowed to stand at 135 ° C. and 1.2 MPa for 30 minutes in an autoclave to produce laminated glass (6 sheets in total). The obtained laminated glass was evaluated according to the method shown in the penetration resistance test of JIS R 3212 (automotive safety glass test method) and JIS R 3211 (automotive safety glass). That is, after the laminated glass was temperature-controlled at 23 ° C. for 4 hours, it was placed horizontally on a dedicated support frame, and a steel ball having a mass of 2260 g and a diameter of 82 mm was freely dropped from a height of 4 m onto the central portion of the laminated glass. When the steel ball penetrated within 5 seconds after the collision, it was determined as “penetration”. Six laminated glasses were tested, and if all did not penetrate, it was determined to be acceptable. In the case where there were 5 pieces that did not penetrate, a retest was conducted. If all 6 pieces did not penetrate, the test was accepted. The results are shown in Table 14.

(Calculation of absolute difference in refractive index of interlayer film for laminated glass and light diffusing fine particles)
50 parts by weight of PVB-1 powder, 19 parts by weight of triethylene glycol-di-2-ethylhexanoate as a plasticizer and 0.014 parts by weight of magnesium acetate were used. Was melt kneaded at 160 ° C. and 50 rpm for 5 minutes. During melt kneading, nitrogen (100 mL / min) was continuously blown into the container. Using the obtained kneaded material, an interlayer film base material for laminated glass containing PVB-1 was obtained in the same manner as described above (production of interlayer film for laminated glass). The refractive index of the interlayer substrate for laminated glass was measured by using an Abbe refractometer manufactured by Atago Co., Ltd., and the absolute difference between the obtained refractive index and the refractive index of the light diffusing fine particles was calculated. The evaluation results are shown in Table 14.

(Measure haze)
The same thing as the intermediate film for laminated glasses produced using the repetitive kneaded material-1 described in the section of “Coloring resistance of interlayer film for laminated glass” was produced. And the laminated glass was produced using the said intermediate film similarly to the production method of the laminated glass described in the term "The foreign material in the intermediate film for laminated glasses". The haze of the laminated glass was measured according to JIS K 7105 using a haze meter “HZ1” manufactured by Suga Test Instruments Co., Ltd. The evaluation results are shown in Table 14.
In addition, using the interlayer film for laminated glass prepared in the section “Preparation of interlayer film for laminated glass”, lamination is performed in the same manner as the method for producing laminated glass described in the section “Foreign matter in interlayer film for laminated glass”. Glass was produced. The haze is measured in the same manner as described above, and the difference between the haze of the laminated glass using the interlayer film for laminated glass produced using the repetitively kneaded product-1 and the measured haze is taken, and the increase in haze is 0. Less than .3 was acceptable, and more than 0.3 was unacceptable. The evaluation results are shown in Table 14.

(Evaluation of the brightness of laminated glass)
The same thing as the intermediate film for laminated glasses produced using the repetitive kneaded product-1 described in the section of “Interlayer film for laminated glass” is prepared, and the section “Foreign matter in interlayer film for laminated glass” A laminated glass was produced in the same manner as the laminated glass production method described in 1. above. The following point light sources were arranged on two opposite sides of the laminated glass to form a surface light emitter, and the brightness at the time of lighting was evaluated in five stages by visual evaluation. The most excellent one was A, and the worst one was E. The evaluation results are shown in Table 14.
Light source: White LED “NS2W157ART-H3” manufactured by Nichia Corporation
Number used: 20 per side Placement interval: 10 mm
Applied voltage: 2.8V / 1 light source

Examples 2-9, Comparative Examples 1-7
An interlayer film for laminated glass in the same manner as in Example 1 except that PVB shown in Table 14 was used instead of PVB-1 and that the addition amount of titanium oxide fine particles “JR-1000” was changed to that shown in Table 14 Were prepared and evaluated. The results are shown in Table 14.

  In Table 14, the interlayer films for laminated glass of Examples 1 to 9 have less foreign matter (undissolved content) in the interlayer film for laminated glass, and are excellent in coloring resistance of the interlayer film for laminated glass. Laminated glass manufactured using a film is excellent in penetration resistance, transparency and light diffusivity, and even when an interlayer film for laminated glass made of a kneaded product that has been repeatedly heated is used, the increase in haze is suppressed. there were. On the other hand, the performance of any of the interlayer films for laminated glass of Comparative Examples 1 to 7 that did not satisfy the conditions defined in the present invention decreased.

Examples 10-12, Comparative Example 8
The titanium oxide fine particle “JR-1000” manufactured by Teika Co., Ltd. was changed to the titanium oxide fine particle “JR-301” (refractive index 2.72) manufactured by Teica Co., Ltd. Production and evaluation of an interlayer film for laminated glass were carried out in the same manner as in Example 1 except for changing to those shown. The results are shown in Table 15.

  In Table 15, the interlayer films for laminated glass of Examples 10 to 12 have less foreign matter (undissolved content) in the interlayer film for laminated glass, and are excellent in the coloring resistance of the interlayer film for laminated glass. Laminated glass manufactured using a film is excellent in penetration resistance, transparency and light diffusivity, and even when an interlayer film for laminated glass made of a kneaded product that has been repeatedly heated is used, the increase in haze is suppressed. there were. On the other hand, any performance of the interlayer film for laminated glass of Comparative Example 8 that does not satisfy the conditions defined in the present invention was lowered.

Examples 13 to 15 and Comparative Example 9
The titanium oxide fine particles “JR-1000” manufactured by Teika Co., Ltd. were changed to the zinc oxide fine particles “Zinc oxide 1 type” (refractive index 1.95) manufactured by Sakai Chemical Industry Co., Ltd., and the amount of “Zinc oxide 1 type” added. The interlayer film for laminated glass was produced and evaluated in the same manner as in Example 1 except that the values were changed to those shown in Table 16. The results are shown in Table 16.

Comparative Example 10
An interlayer film for laminated glass in the same manner as in Example 1 except that the titanium oxide fine particles “JR-1000” manufactured by Teika Co., Ltd. were changed to calcium carbonate fine particles Hydrocarb 95T-OG (refractive index: 1.59) manufactured by Omya GmbH. Were prepared and evaluated. The results are shown in Table 16.

  In Table 16, the interlayer films for laminated glass of Examples 13 to 15 have less foreign matter (undissolved content) in the interlayer film for laminated glass, and are excellent in coloring resistance of the interlayer film for laminated glass. Laminated glass manufactured using a film is excellent in penetration resistance, transparency and light diffusivity, and even when an interlayer film for laminated glass made of a kneaded product that has been repeatedly heated is used, the increase in haze is suppressed. there were. On the other hand, the performance of any of the interlayer films for laminated glass of Comparative Examples 9 to 10 that did not satisfy the conditions defined in the present invention decreased.

Example 16, Comparative Examples 11-12
An interlayer film for laminated glass was produced and evaluated in the same manner as in Example 1 except that PVB shown in Table 17 was used instead of PVB-1. The results are shown in Table 17.

In Table 17, the interlayer film for laminated glass of Example 16 has few foreign matters (undissolved content) in the interlayer film for laminated glass, and has excellent coloration resistance of the interlayer film for laminated glass. The laminated glass produced using this was excellent in penetration resistance, transparency and light diffusibility, and even when an interlayer film for laminated glass made of a kneaded material repeatedly heated was used, the increase in haze was suppressed. . On the other hand, any performance of the interlayer films for laminated glass of Comparative Examples 11 to 12 that did not satisfy the conditions defined in the present invention was lowered.

Example 17, Comparative Examples 13-15
An interlayer film for laminated glass was produced and evaluated in the same manner as in Example 1 except that PVB shown in Table 18 was used instead of PVB-1. The results are shown in Table 18.

  In Table 18, the interlayer film for laminated glass of Example 17 has little foreign matter (undissolved content) in the interlayer film for laminated glass, and is excellent in coloring resistance of the interlayer film for laminated glass. The laminated glass produced using this was excellent in penetration resistance, transparency and light diffusibility, and even when an interlayer film for laminated glass made of a kneaded material repeatedly heated was used, the increase in haze was suppressed. . On the other hand, the performance of any of the interlayer films for laminated glass of Comparative Examples 13 and 14 decreased. In Comparative Example 15, the viscosity was too high to obtain an interlayer film for laminated glass.

Examples 18-22, Comparative Examples 16-18
An interlayer film for laminated glass was produced and evaluated in the same manner as in Example 1 except that PVB shown in Table 19 was used instead of PVB-1. The results are shown in Table 19.

  In Table 19, the interlayer films for laminated glass of Examples 18 to 22 have less foreign matter (undissolved content) in the interlayer film for laminated glass, and are excellent in coloring resistance of the interlayer film for laminated glass. Laminated glass manufactured using a film is excellent in penetration resistance, transparency and light diffusivity, and even when an interlayer film for laminated glass made of a kneaded product that has been repeatedly heated is used, the increase in haze is suppressed. there were. On the other hand, any performance of the interlayer films for laminated glass of Comparative Examples 16 to 18 that did not satisfy the conditions defined in the present invention was lowered.

Example 23, Comparative Examples 19-20
An interlayer film for laminated glass was produced and evaluated in the same manner as in Example 1 except that PVB shown in Table 20 was used instead of PVB-1. The results are shown in Table 20.

  In Table 20, the interlayer film for laminated glass of Example 23 has little foreign matter (undissolved content) in the interlayer film for laminated glass, and excellent in the coloration resistance of the interlayer film for laminated glass. The laminated glass produced using this was excellent in penetration resistance, transparency and light diffusibility, and even when an interlayer film for laminated glass made of a kneaded material repeatedly heated was used, the increase in haze was suppressed. . On the other hand, any performance of the interlayer films for laminated glass of Comparative Examples 19 to 20 that did not satisfy the conditions defined in the present invention was lowered.

Example 24, Comparative Examples 21-22
An interlayer film for laminated glass was produced and evaluated in the same manner as in Example 1 except that PVB shown in Table 21 was used instead of PVB-1. The results are shown in Table 21.

  In Table 21, the interlayer film for laminated glass of Example 24 has less foreign matter (undissolved content) in the interlayer film for laminated glass, and has excellent coloration resistance of the interlayer film for laminated glass. The laminated glass produced using this was excellent in penetration resistance, transparency and light diffusibility, and even when an interlayer film for laminated glass made of a kneaded material repeatedly heated was used, the increase in haze was suppressed. . On the other hand, the performance of any of the interlayer films for laminated glass of Comparative Examples 21 to 22 that did not satisfy the conditions defined in the present invention decreased.

Claims (12)

An interlayer film for laminated glass containing polyvinyl acetal, having an acetalization degree of 60 to 80 mol%, a vinyl ester monomer unit content of 0.1 to 20 mol%, and a viscosity average polymerization degree of 1400 to 4000 And the absolute value of the difference between the refractive index of the light diffusing fine particles and the refractive index of the composition obtained by removing the light diffusing fine particles from the composition. It is 0.20 or more, and the haze measured by a method based on JIS K 7105 when sandwiching the interlayer film for laminated glass between two glass plates having a thickness of 3 mm to form laminated glass is 20% or less. An interlayer film for laminated glass that is present and satisfies the following formulas (1) and (2).
(AB) / A <0.80 (1)
1.00 × 10 ⁻² <(b / y) / (a / x) <2.00 × 10 ⁻¹ (2)
In the formula, A, a, B, b, x, and y are as follows.
A: Peak top molecular weight of a polymer component measured by a differential refractive index detector when the interlayer film for laminated glass heated at 230 ° C. for 3 hours was measured by gel permeation chromatography a: Peak top molecular weight (A) Signal intensity B: The peak top molecular weight b of the polymer component measured with an absorptiometric detector (measurement wavelength 280 nm) when the interlayer film for laminated glass heated at 230 ° C. for 3 hours was measured by gel permeation chromatography : Signal intensity at peak top molecular weight (B) x: Signal intensity at peak top molecular weight measured with differential refractive index detector when monodisperse polymethyl methacrylate is measured by gel permeation chromatography y: Monodispersion Of polymethyl methacrylate Upon permeation chromatography measurement, the signal intensity at the peak top molecular weight measured by spectrophotometric detector (measurement wavelength 220 nm) Furthermore, the intermediate film for laminated glasses of Claim 1 which satisfy | fills following formula (3) and (4).
(AC) / A <0.80 (3)
5.00 × 10 ⁻³ <(c / y) / (a / x) <7.00 × 10 ⁻² (4)
In the formula, A, a, C, c, x, and y are the following values.
A: a, x, y the same as the above formula (1) C: the same as the above formula (2) C: Absorbance when the interlayer film for laminated glass heated at 230 ° C. for 3 hours is measured by gel permeation chromatography Peak top molecular weight c of the polymer component measured by a photometric detector (measurement wavelength: 320 nm): signal intensity at peak top molecular weight (C).   The interlayer film for laminated glass according to claim 1 or 2, wherein the polyvinyl acetal is polyvinyl butyral.   Furthermore, the intermediate film for laminated glasses in any one of Claims 1-3 containing a plasticizer.   The interlayer film for laminated glass according to claim 4, comprising triethylene glycol-di-2-ethylhexanoate as a plasticizer.   The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the light diffusing fine particles are an inorganic compound.   The interlayer film for laminated glass according to claim 6, wherein the inorganic compound is a metal oxide.   The interlayer film for laminated glass according to claim 7, wherein the metal oxide is titanium oxide.   The interlayer film for laminated glass according to claim 7, wherein the metal oxide is zinc oxide.   The interlayer film for laminated glass according to any one of claims 6 to 9, wherein the content of the light diffusing fine particles is 0.001 to 0.040 mass% in the composition constituting the interlayer film for laminated glass.   The laminated glass formed by adhere | attaching a several glass plate using the intermediate film for laminated glasses in any one of Claims 1-9.   The light diffusing plate which has the laminated glass of Claim 11 as a structure.

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